Hydrocarbons MODULE - 7

Chemistry of Organic
Compounds

24
Notes
HYDROCARBONS

You have studied in the previous lesson that hydrocarbons are the compounds
containing carbon and hydrogen. You also know that they are classified as aliphatic,
alicyclic and aromatic hydrocarbons. They constitute a very important class of
organic compounds and are widely used as fuels, lubricants and dry cleaning
agents. They are also used as important ingredients in medicines and in dyes.
Petroleum and coal are the major sources of various types of hydrocarbons. The
products obtained from fractional distillation of petroleum and destructive
distillation of coal are used almost in every sphere of life. Hydrocarbons are
considered to be the parent organic compounds, from which other organic
compounds can be derived by replacing one or more hydrogen atoms with different
functional groups. In this lesson, you will study about the preparation, important
physical and chemical properties of hydrocarbons.

OBJECTIVES
After reading this lesson, you will be able to :
z list different methods of preparation of alkanes;
z explain the reasons for variation in physical properties of alkanes;
z draw the conformations of ethane and compare their relative stability;
z describe different chemical properties of alkanes;
z list different methods of preparation of alkenes;
z explain the physical properties of alkenes;
z describe the chemical properties of alkenes;
z list different methods of preparation of alkynes;
z explain physical and chemical properties of alkynes;
z discuss the cause of greater reactivity of alkenes and alkynes over alkanes;

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Compounds z distinguish alkanes, alkenes and alkynes;
z list various fractions obtained by destructive distillation of coal;
z explain the stability of various aromatic compounds using resonance;
z state Huckel rule and its use;
z describe methods of preparation, physical properties and chemical properties
of benzene;
Notes
z list various uses of hydrocarbons; and
z explain the term carcinogenicity and Toxicity.

24.1 ALKANES (PARAFFINS)

Alkanes are saturated hydrocarbons. They are very less reactive towards various
reagents; hence, they are also referred to as paraffins (parum means little, affins
means affinity).

24.1.1 Methods of Preparation

Some important methods of preparation of alkanes are as follows:
1. From Haloalkanes (Alkyl Halides ): Monohaloalkanes can be converted
to alkanes by following three methods :
a) By reduction of haloalkanes: The replacement of halogen atom of
haloalkanes with hydrogen is called the reduction and can be carried out
by the following reagents :
(i) Zinc and dilute HCl

CH3Br + Zn + 2 HCl ⎯⎯→ CH4 + ZnCl2 + HBr

Bromomethane Methane

(ii) HI in the presence of red phosphorus

red phosphorus
C2 H5 I + HI ⎯⎯⎯⎯⎯⎯⎯
→ C 2 H 6 + ZnCl2 + HBr
423 K
Iodoethane Methane

(iii) Catalytic reduction

Pt (catalyst)
CH3Cl + H 2 ⎯⎯⎯⎯⎯⎯
→ CH 4 + HCl
Chloromethane Methane

b) By using Grignard’s Reagent : A Grignard reagent is a compund of the

type RMgX which is prepared by reacting a haloalkane with magnesium
metal in the presence of dry ether.
dry ether
C 2 H5 Br + Mg ⎯⎯⎯⎯⎯
→ C 2 H5 MgBr
Bromoethane Ethyl Magnesium Bromide

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The Grignard’s reagents are used to prepare various compounds like Compounds
hydrocarbons, ethers, alcohols and carboxylic acids. It reacts with the
compounds containing active hydrogen and forms alkanes. An easily
replaceable hydrogen atom present in the compounds is called active
hydrogen. An active hydrogen is present in (i) alcohols and (ii) water and
(iii) acids.
CH3MgBr + C2H5OH → CH4 + Mg(OC2H5)Br Notes
C2H5MgBr + H2O → C2H6 + Mg(OH)Br
c) By Wurtz Reaction : In this reaction, an alkyl halide reacts with sodium
metal in the presence of dry ether and forms the higher alkanes.

dry ether
CH3 − Br + 2 Na + Br − CH3 ⎯⎯⎯⎯⎯
→ CH3 − CH3 + 2 NaBr
Bromoethane Ethane

2. From Unsaturated Hydrocarbons : The unsaturated hydrocarbons (i.e.

alkenes and alkynes) can be converted to alkanes by the addition of hydrogen
in the presence of a catalyst like nickel, platinum or palladium.
Ni or Pt
CH 2 = CH 2 + H 2 ⎯⎯⎯⎯
573 K
→ CH3 – CH3

CH ≡ CH + 2H 2 ⎯⎯
Ni or Pt
⎯ ⎯→ CH 3 – CH 3
573 K

This reaction is also called hydrogenation and is used to prepare vegetable

ghee from edible oils (by converting unsaturated fats to saturated ones.)
3. From Alcohols, Aldehydes and Ketones : Alcohols, aldehydes and ketones
on reduction with HI, in presence of red phosphorus, give alkanes.The general
reactions are as shown below.
ROH + 2HI ⎯⎯⎯⎯⎯
→ RH + I 2 + H 2 O
red P / 423K
Alcohol Alkane

RCHO + 4HI ⎯⎯⎯⎯⎯

→ RCH 3 + 2 I 2 + H 2 O
red P / 423K
Aldehyde Alkane

RCOR ′ + 4HI ⎯⎯⎯⎯⎯

→ RCH 2 R ′ + 2 I 2 + H 2 O
red P / 423K

Ketone Alkane

4. From Carboxylic Acids : Carboxylic acids can produce alkanes in a number

of ways as shown below :
CaO
i) Heating with soda lime : RCOONa + NaOH ⎯⎯⎯→ RH + Na2CO3
Δ
In this reaction, an alkane with one carbon less than those present in the
parent carboxylic acid is obtained.

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Compounds ii) By Reduction of carboxylic acid:
red P / 423 K
RCOOH + 6 HI ⎯⎯⎯⎯⎯⎯
→ RCH3 + 3 I 2 + 2H 2 O

Here, an alkane with same number of carbon atoms as in the starting

carboxylic acid is obtained.

Notes iii) Kolbe’s Electrolysis: Sodium or potassium salt of a carboxylic acid, on

electrolysis, gives a higher alkane. The reaction takes place as follows.

⎯⎯⎯⎯⎯→ RCOO − + Na +
electrolysis
RCOONa
Sodium salt of carboxylic acid Anion Cation

At Anode :

RCOO − ⎯⎯
→ RCOO• + e −

RCOO• ⎯⎯
→ R • + CO 2

R • + R • ⎯⎯
→R −R

Thus, ethane can be obtained by the electrolysis of sodium ethonate.

2 CH3COONa ⎯⎯
→ CH3 − CH3
Sodium ethanote Ethane (at anode)

Note that the alkanes with even number of carbon atoms can easily be
prepared by this method.

24.1.2 Physical Properties of Alkanes

Physical State: The physical state of alkanes depends upon the intermolecular
forces of attraction present between molecules which in turn, depend upon the
surface area of the molecules. As the molecular mass of the alkanes increases,
their surface area also increases, which in turn, increases the intermolecular
forces of attraction, and accordingly, the physical state of alkanes changes from
gaseous to liquid, and then to solid. The alkanes containing 1 to 4 carbon atoms
are gases, whereas those containing 5 to 17 carbon atoms are liquids, and the still
higher ones are solids. In the case of isomeric alkanes, the straight chain alkanes
will have maximum surface area, and hence, stronger intermolecular force of
attraction. As the branching increases, surface area decreases. Hence the
intermolecular forces of attraction decrease. Let us consider the isomers of pentane
(C5H12).
CH3 — CH2 — CH2 — CH2 — CH3
n-Pentane

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CH3 Compounds
CH3 — CH2 — CH — CH3
2-Methylbutane (Isopentane)

CH3

CH3 — C — CH3

CH3 Notes
2,2-Dimethylpropane (Neopentane)

Amongst these three isomeric compounds, neopentane will have the weakest
intermolecular forces of attraction due to the smallest surface area of its molecules.
Density: The density of alkanes increases with the increase in molecular mass
which increases with the increase in the number of carbon atoms. All alkanes are
lighter than water i.e. their density is less than 1.0 g/cm3. The maximum density
in the case of alkanes is 0.89 g cm3. The lower density of alkanes than water is
due to the absence of strong intermolecular attractions in alkanes.
Boiling Point: The boiling points of alkanes also increase with the increase in
the molecular mass. In straight chain alkanes, the increase in boiling points due
to the increase in surface area of the molecules. Branching in a chain reduces the
surface area and therefore, decreases the boiling point of alkanes. Thus, in the
above example, isopentane and neopantane have a lower boiling point than pentane.
Melting Point:Similar to the boiling points, the melting points of alkanes also
increase with the increase in their molecular mass, but there is no regular variation
in melting point. The melting points of alkanes depend not only upon the size and
shape of the molecules, but also on the arrangement (i.e. the packing) of the
molecules in the crystal lattice.
In alkanes, each carbon atom is sp3 hybridized which results in a bond angle of
109°28′. In straight chain hydrocarbons the carbon atoms are arranged in a zig-
zag way in the chain. If the molecule contains an odd number of carbon atoms,
then the two terminal methyl groups lie on the same side. So the interaction
between the alkane molecules, with odd number of carbon atoms, is less than the
molecule with even number of carbon atoms, in which terminal methyl groups lie
on the opposite sides.
CH2 CH2 CH2 CH2 CH3 CH2 CH2 CH2
CH3 CH CH3 CH3 CH2 CH2 CH3 CH2 CH2 CH3
2
n-Pentane n-Hexane n-Heptane
(Carbon atoms = 5, m.p.142 K) (Carbon atoms =6, m.p. = 179 K)(carbon atoms = 7, m.p. = 183 K)

In the above structures, we find that alkanes containing even number of carbon
atoms are more symmertical and can be more closely packed as compared with

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Compounds alkanes containing odd number of carbon atoms and can be more closely packed.
Van der Waal’s force of attraction is stronger, due to which they have higher
melting points. Therefore, the alkanes with odd number of carbon atoms have
lower melting point than those having even number of carbon atoms.

24.1.3 Conformations of Ethane

Notes You have studied section 25.3.2 that electronic displacements affect the physical
and chemical properties of organic compounds. You will now study how the
forces present within the molecules affect their structures and stabilities. In fact,
these interactions make some geometric arrangements of atoms energetically more
favorable than others.
In ethane molecule, C2H6, the two carbon atoms are linked together by a single
bond called sigma (σ) bond.
sigma (σ) bond
↓
H3C — CH3
ethane
If we make a model of ethane molecule showing the C — C bond and the hydrogens
attached to carbon atoms, it will look like as follows :

Hydrogen atom

Carbon atom

Model of ethane molecule

The groups bonded through a sigma bond can easily rotate with respect to each
other. i.e. the two — CH3 groups in ethane can rotate with respect to each other.
The different arrangement of atoms resulting from such a rotation are called
conformations and each such specific conformation is called a conformer (from
conformational isomer).
The conformational isomers can be represented in the following two ways:
(i) Sawhorse representations
(ii) Newman projections
The Sawhorse representations show the carbon–carbon bond from an oblique
angle and indicate the spatial arrangement of all C — H bonds.

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H Compounds
H
C

H H

Notes
C
H
H

Sawhorse Projections

In Newman projections the two carbon atoms are viewed along the C — C
bond axis. The front carbon and its bonds are represented as whereas the back
carbon and its bonds are represented as .
H
Back Hydrogen
H H

Back Carbon Front Carbon

H H Front Hydrogen

H
Newman Projection
The Newman projections are easier to draw and in such drawings, the relative
positions of atoms are easily visualised. Therefore, we will use Newman projec-
tions to study the conformations of ethane.
Several conformations of ethane are possible. But, there are two extreme possi-
bilities. These are discussed below:
(i) In this conformation all the six C — H bonds are as far away as possible.
This conformation is called staggered conformation and is shown below:
H

H H

H H

H
Staggered conformation of ethane

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Compounds (ii) Another conformation in which all the six C — H bonds are as close as
possible is shown below:
H H

Notes H
H
H
H

Eclipsed conformation of ethane

This is called eclipsed conformation. The three rear hydrogens are drawn little
more rotated than the perfectly eclipsed positions to make them visible in the
structure.
Remember that there are infinite number of possible conformations in between
the staggered and the eclipsed conformations. All these conformations originate
by the rotation of the C — C bond.
The staggered conformation is the most slable conformation whereas the eclipsed
conformation is the least stable conformation of ethane. The eclipsed conforma-
tion has about 12 kJ mol–1 higher energy than the staggered conformation.

24.1.4 Chemical Properties of Alkanes

1. Halogenation reactions: The chemical reactions in which a hydrogen atom of
an alkane is replaced by a halogen atom are known as halogenation. Alkanes
react with chlorine in the following way.
Diffused Sunlight
CH 4 + Cl2 ⎯⎯⎯⎯⎯⎯⎯⎯ → CH3Cl
− HCl
Methane Chloromethane

CH3Cl + Cl2 ⎯⎯⎯→

− HCl CH2Cl2
Dichloromethane

CH2Cl2 + Cl2 ⎯⎯⎯→

− HCl CHCl3
Trichloromethane

CHCl3 + Cl2 ⎯⎯⎯→

− HCl CCl4
Tetrachloromethane

Chlorination of methane takes place via the free radical mechanism. When the
reaction mixture is exposed to sunlight, chlorine molecules absorb energy from
sunlight and get converted to free radicals i.e. chlorine atoms with an unpaired
•
electron (Cl) . The chlorine radicals then combine with methane and form methyl
•
radical [CH 3 ] . The methyl radical further reacts with chlorine molecule and

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produces chloromethane. This reaction continuously takes place till it is stopped Compounds
or the reactants completely react to form the products. The free radical mechanism
involves the following three steps.
(i) Chain Initiation Step: It involves the formation of free radicals.
hν
Cl2 ⎯⎯→ 2Cl• (hv = energy of light)
(ii) Chain Propagation Step : The free radicals give rise to the formation of Notes
more free radicals as is shown in the following reaction.
• •
CH 4 + Cl ⎯⎯
→ CH3 + HCl

• •
CH3 + Cl2 ⎯⎯
→ CH3Cl + Cl
(iii) Chain Termination Step : In this step, free radicals combine with one another
and the further reaction stops.
• •
CH3 + Cl ⎯⎯
→ CH3Cl
• •
Cl + Cl ⎯⎯
→ Cl2
• •
CH 3 + CH 3 ⎯⎯
→ CH 3 − CH 3
The reactivity of halogens is in the order of F2 > Cl2 > Br2 > I2.
2. Oxidation: Alkanes undergo oxidation (combustion) in excess of oxygen
and produce carbon dioxide and water. This reaction is highly exothermic in
nature.For example :
→ CO 2 + 2 H 2 O + 890 KJ mol −1
CH 4 + 2 O 2 ⎯⎯
If the combustion is carried out in the presence of an insufficient supply of air
or O2, then incomplete combustion takes place forming carbon monoxide
instead of carbon dioxide.
heat
2C 2 H 6 + 5O 2 ⎯⎯⎯ → 4CO + 6H 2 O
3. Cracking or Pyrolysis: At very high temperature and in the absence of air,
the alkanes break apart into smaller fragments. For example,
873 K
CH3 − CH 2 − CH 3 ⎯⎯⎯→ CH 3CH = CH 2 + H 2
or CH2 = CH2 + CH4
4. Isomerisation : n-Alkanes, in the presence of aluminium halide and HCl, are
converted to their branched isomers.
CH3
AlCl / HCl
CH3 − CH 2 − CH 2 − CH3 ⎯⎯⎯⎯⎯
3
⎯
→ CH3 — CH — CH3
n -butane isobutane

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Compounds 24.1.4 Uses of Alkanes
Alkanes are used as fuel gases, solvents, drycleaning agents, lubricants and in
ointments (paraffin wax). Methane is used for illuminating and domestic fuel and
also for the production of other organic compounds such as haloalkanes, methanol,
formaldehyde and acetylene. Propane is used as a fuel, refrigerant and as raw
material in the petrochemical industry. Butane and its isomer–isobutane, are the
Notes major constituents of LPG .

INTEXT QUESTIONS 24.1

1. List four important uses of hydrocarbons.
2. What is Grignard’s reagent in a molecule?
3. What is an active hydrogen in a molecule?
4. What makes the physical properties of various hydrocarbons different?
5. Name two alkanes which are gases and two alkanes which are liquids at
room temperature.
6. Name three isomers of pentane.
7. Which one has higher b.p. n-butane or n-pentane? Explain.
8. Write the balanced chemical equation for the complete combustion of propane.

24.2 Alkenes
These are unsaturated hydrocarbons containing at least one double bond between
two carbon atoms. The hydrocarbons of this class are also called olefines (olefiant
= oil forming).

24.2.1 Methods of Preparation

In the laboratory, alkenes are generally prepared either from haloalkanes (alkyl
halides) or alcohols.
1. From Haloalkanes: Halaoalkanes are converted to alkenes by
dehydrohalogenation. The process of removal of halogen acid like HCl, HBr or
HI from the adjacent carbon atoms of alkyl halides, when reacted with alcoholic
solution of potassium hydroxide, is called dehydrohalogenation.
CH3 — CH2 — Cl + KOH(alc.) → CH2 = CH2 + KCl + H2O
Chloroethane Ethene

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2KOH(alc.) Compounds
CH3CH2CHCH3 CH3CH = CHCH3 + CH3CH2CH = CH2
But-2-ene (Major) But-1-ene (Minor)
Cl
2-Chlorobutane

The major product is formed according to the Saytzeff’s Rule.

Saytzeff’s Rule : It states that when an alkyl halide reacts with alcoholic
solution of potassium hydroxide and if two alkenes are possible, then the one Notes
which is more substituted, will be the major product. In the above example,
but-2-ene is the major product because it contains two alkyl groups attached to
the –C=C– group.
2. From Alcohols : Alkenes can be prepared from alcohols by dehydration in the
presence of a suitable dehydrating agent such as (i) Al2O3 or (ii) concentrated
H2SO4.
Al O
CH3 − CH 2 − OH ⎯⎯⎯⎯⎯
2 3
→ CH 2 = CH 2 + H 2O
623 − 633K
Ethanol Ethene

conc. H SO
CH3 − CH 2 − OH ⎯⎯⎯⎯⎯⎯
2 4
→ CH 2 = CH 2 + H 2O
433K
Ethanol Ethene
In the dehydration of higher alcohols, the major product obtained is according to
the Saytzeff’s Rule.

24.2.2 Physical Properties of Alkenes

Some important physical properties of alkanes are as follows:
Physical State : Unbranched alkenes containing upto four carbon atoms are
gases and containing five to sixteen carbon atoms are liquids while those with
more than 16 carbon atoms are solids.
Boiling Points : The boiling points of alkenes increase with molecular mass as is
shown in Table 24.1.
Table 24.1 : Boiling points of Alkenes
Alkene Ethene Propene But-1-ene Pent-1-ene Hex-1-ene
b.p. (K) 169 226 267 303 337

The increase in boiling point can be attributed to the van der Waals forces which
increases with number of carbon atoms of the alkene. The branched chain alkenes
have lower boiling points than those of straight chain isomers.
Melting Point : In alkenes, there is increase in the melting point with the increase
in molecular mass. In the case of isomeric alkenes, the cis and trans isomers have
different melting points.

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Compounds For example

CH3 H CH3 CH3

C=C C=C
H CH3 H H

trans-But-2-ene cis-But-2-ene
Notes (m.p. 167 K) (m.p. = 134 K)

24.2.3 Chemical Properties of Alkenes

1. Addition Reactions : The chemical reactions in which a molecule adds to
another molecule are called an addition reaction. These reactions are
characteristic of unsaturated compounds like alkenes and alkynes. The
following reactions illustrate the addition reactions of alkenes.
(i) Addition of Hydrogen : Addition of hydrogen to unsaturated
hydrocarbons takes place in the presence of a catalyst like Ni, Pt or Pd.

Ni (Pt or Pd)
CH 2 = CH 2 + H 2 ⎯⎯⎯⎯⎯⎯
→ CH3 − CH3
573K
Ethene Ethane

(ii) Addition of Halogens : Halogens on addition to alkenes, form 1,2-

dihaloalkanes.

CH2 = CH2 + Br2 (in CCl4) ¾¾® CH2 – CH2

Ethene
Br Br
1, 2-Dibromoethane

As a result of this addition reaction, the reddish-brown colour of Br2

gets discharged. This reaction is also used as test for unsaturation in
hydrocarbons.
(iii) Addition of Halogen Acids (HX) : When halogen acids are added to
alkenes , hydrogen adds to one carbon atom whereas halogen atom
adds to the second carbon atom of the double bond.

CH2 = CH2 + HBr ⎯⎯

→ CH3 – CH2 – Br
Ethene Bromoethane

In case of unsymmetrical alkenes (which contain unequal number of H-

atoms attached to the carbon atoms of the double bonds), the addition
of HX takes place according to the Markownikoff’s rule. This rule
states that in the addition of halogen acids to unsymmetrical alkenes,
the halogen of HX goes to that carbon atom of C = C bond which
already has less H-atoms attached to it. In other words, hydrogen

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atom of HX goes to the carbon atom with more number of H-atoms Compounds
attached to it.
CH3CH = CH2 + HBr ⎯⎯
→ CH3CHBr CH3
Propene 2-Bromopropane

Mechanism of Electrophilic Addition: You have studied earlier that

the electron cloud of the pi bond is present above and below the plane
of the molecule in alkenes. Various electron seeking species and Notes
reagents thus react with the alkenes. For example, H+ of HX(HBr) can
add to the double bond to yield a carbocation.

H Br

H H H
+ Br–
C C ¾¾® C C ¾¾®

H H
Carbocation

H Br

C C

alkyl halide
The carbocation being highly reactive reacts with the halide ion in the
second step to yield an alkyl halide (alkyl bromide).
In case, the starting alkene is unsymmetrical e.g. propene, then in the
first step of formation of a carbocation, there are two possibilities of
attachment of H+ of HX which are shown below:
H
CH2 ¾¾® CH3 CH CH2 + :X:–
: :

: :

:X H CH3 OH
(I) primayr
carbocation
(less stable)

+
X: ¾¾® CH3 CH H + :X:–
: :

: :

CH3 OH CH2 + H CH2

(II) secondary
carbocation
more stable
This would lead to the formation of two carbocations as shown above.
The two possible carbocations have different stabilities i.e. the second-
ary carbocation (II) is more stable than the primary carbocation (I).
Therefore, the secondary carbocation (II) is formed preferentially in
the first step. Further reaction, i.e. attack of Br– on the carbocation,
thus yields 2-bromopropane as the major product.

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Compounds + –
CH3CH CH3 Br® CH CH CH
¾ 3 3
H fast
Br
2-bromopropare
(main product)
HBr
CH3CH = CH2 slow –
+ Br
X CH3CH CH2 ¾ ® CH3CH2CH2Br
1-bromopropare
Notes little amount

Thus, the above explanation describes for the formation of 2-

bromopropane as the major product as per the Markownikoff’s rule.
If the addition of HBr is carried out in the presence of peroxides such as
benzoyl peroxide, then the reaction takes place contrary to
Markownikoff’s rule. This is also known as Anti-Markownikoff’s
addition or peroxide effect.

benzoyl peroxide
CH3CH = CH2 + HBr ⎯⎯⎯⎯⎯⎯⎯
→ CH3CH2 – CH2 – Br
Propene 1 – Bromopropane

(iv) Addition of Water : Addition of water takes place in the presence of

mineral acids like H2SO4.
H SO
CH2 = CH2 + H2O ⎯⎯⎯⎯
2 4
Heat
→ CH3 – CH2 – OH

Ethene Ethanol

(v) Addition of H2SO4

CH2 = CH2 + conc. H2SO4 ⎯⎯
→ CH3 – CH2 – HSO4
Ethene Ethyl hydrogen sulphate

(vi) Addition Polymerization : The process in which many molecules of

an alkene add together to form a larger molecule is called addition
polymerization.

n (CH2=CH2) ⎯⎯⎯⎯⎯⎯
heat , pressure
→ ( – CH2 – CH – ) n
2

Ethene Polyethene

2. Oxidation : The oxidation of alkenes can be done by using different oxidizing

agents like KMnO4, oxygen and ozone.
(i) Oxidation with KMnO4
Alkenes are unsaturated hydrocarbons having Pi (π)-bond(s) between
the carbon atoms, so they are easily oxidized by cold dilute alkaline
solution of KMnO4.

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CH2 – OH Compounds
CH2
KMnO4
⎯⎯⎯⎯⎯ ⎯→
CH2 cold alkaline CH2 – OH
Ethene Ethanediol

When an alkaline solution of KMnO4 (Baeyer’s Reagent) is added to an

alkene, the purple colour of KMnO4 gets discharged. This reaction is
used to test unsaturation in hydrocarbons. On treatment with hot alkaline Notes
KMnO4 the alkene gets oxidized to ketones or further to acids depending
upon its structure. This happens due to the breaking of carbon-carbon
double bond.

CH3
CH3
alk. KMnO 4
CH3 – C = CH2 + 3[O] ⎯⎯⎯⎯⎯⎯hot
→ C=O + HCOOH
2-Methylpropene CH3
(Acetone) (Formic Acid)
Propanone Methanoic acid

(ii) Oxidation with Oxygen : Ethene on oxidation with oxygen in the

presence of silver (Ag) gives epoxyethane. The reaction is shown below:
1 585 K
CH 2 = CH 2 + O 2 ⎯⎯⎯⎯ → CH2 – CH2
2 Ag
Ethene O
Epoxyethane

(iii) Combustion : The oxidation reaction, in which carbon dioxide and

water are formed along with the liberation of heat and light, is called
combustion.
heat
CH2 = CH2 + 3 O2 ⎯⎯⎯ → 2 CO2 + 2 H2O ΔH = –1411 KJ mol–1

(iv) Oxidation with Ozone : Ozone adds to the alkene forming ozonide.
The ozonide when further reacted with water in the presence of zinc
dust, forms aldehydes or ketones, or both.

H O H
C C
H H Zn / H O
CH 2 = CH 2 + O3 → O O ⎯⎯⎯⎯
2 ⎯
→ 2HCHO
Ethene Ethene
Ozonide

This process of addition of ozone to an unsaturated hydrocarbon

followed by hydrolysis is called ozonolysis.
Ozonolysis can be used for the determination of the position of double
bonds in alkenes by analysing the products formed i.e. aldehydes and
ketones. This is explained below.

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 MODULE - 7 Hydrocarbons C
Chemistry of Organic
Compounds
4 3 2 1 O
CH3 –CH 2 –CH=CH 2 ⎯⎯→
3 O
CH3CH2– C CH2
But-1-ene O O

Zn / H O
2 → CH CH CHO + HCHO
⎯⎯⎯⎯⎯ 3 2
Propanal Methanal
Notes
When but-1-ene is oxidized with ozone and the ozonide formed is
hydrolysed, we get one mole of propanal and one mole of methanal,
showing that the double bond is between carbon atom 1 and 2. Whereas
but-2-ene on oxidation with ozone, followed by hydrolysis, gives two
moles of ethanal, showing that the double bond is present between carbon
atoms 2 and 3 as shown below.

4 3 2 1 O Zn / H2O
CH3 CH 2 = CH–CH 2 ⎯⎯→ CH − CH 3 ⎯⎯⎯⎯→ 2 CH 3CHO
3 O
CH
Ethanal
But-2-ene
O O

24.2.4 Uses of Alkenes

Ethene is used for making mustard gas, which is a poisonous gas used in warfare.
It is also used for artificial ripening of fruits, as a general anaesthetic and for
producing other useful materials such as polythene, ethanal, ethylene glycol
(antifreeze), ethylene oxide (fumigant) etc.

INTEXT QUESTIONS 24.2

1. Which one has higher boiling point: cis but-2-ene or trans but-2-ene?
2. Name the products formed when ethene is oxidized with cold alkaline solution
of KMnO4.
3. Write the conditions for hydrogenation of alkenes.
4. What happens when ethene reacts with oxygen at 575 K in presence of Ag?

24.3 ALKYNES
These are also unsaturated hydrocarbons which contain atleast one triple bond
between two carbon atoms. Some examples are as follows :

CH ≡ CH, CH 3 − C ≡ CH, CH 3 − C ≡ C − CH 3
Ethyne Propyne But-2-yne

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24.3.1 Preparation of Ethyne (Acetylene) Compounds
Some important methods for preparation of ethyne are explained below.
1. From Calcium Carbide: Ethyne can be prepared in the laboratory, as well as
on a large scale, by the action of water on calcium carbide.

CaC2 + → H – C ≡ C — H + Ca(OH)2
2 H2O ⎯⎯
Calcium carbide Water Ethyne Notes
Ethyne prepared by this method generally contains the impurities of hydrogen
sulphide and phosphine due to the impurities of calcium sulphide and calcium
phosphide in calcium carbide.
2. Preparation of Ethyne from Dihaloalkanes
Ethyne can be prepared by refluxing geminal dihaloalkanes (having both halogens
attached to the same carbon atom) or vicinal dihaloalkanes (having halogen atoms
attached to the adjacent carbon atoms) with alcoholic solution of KOH.
CH2Br CH2 C—H
heat alc. KOH
+ alc. KOH ⎯⎯⎯ → ⎯⎯⎯⎯⎯
→
CHBr heat C—H
CH2Br
1,2-Dibromoethane Vinyl Bromide Ethyne

CH3 CH2 C—H

heat alc. KOH
+ alc. KOH ⎯⎯⎯ → ⎯⎯⎯⎯⎯
→
CHBr heat C—H
CHBr2
1,1-Dibromoethane Vinyl Bromide Ethyne

3. Preparation of higher alkynes : Higher alkynes can be prepared by the reaction

of alkynides of lower alkynes with primary alkyl halides.

→ R − C ≡ C − Na +
liq. NH
R − C ≡ CH + Na ⎯⎯⎯⎯
3
⎯

R − C ≡ C − Na + + CH3I ⎯⎯
→ R − C ≡ C − CH3 + NaI

24.3.2 Physical Properties of Alkynes

1. First three members of alkynes are gases, the next eight members are liquids
and members having more than twelve carbon atoms are solids.
2. They are colourless and odourless, except ethyne which has a garlic odour.
3. The melting points, boiling points and densities of alkynes increase with the
increasing molar mass. In alkynes, there are π(pi)-electrons due to which
these molecules are slightly polar. So charge separation takes place in alkynes,
and hence dipoles are formed. The presence of dipoles increases the inter
molecular force of attraction, and hence the boiling points of alkynes are
higher than those of the corresponding alkanes.
4. Alkynes are very slightly soluble in water and soluble in acetone.

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Compounds 24.3.3 Chemical Properties of Alkynes
1. Addition Reactions : Some of the addition reactions of alkynes are as
follows.
(i) Addition of Hydrogen : Addition of hydrogen to alkynes takes place in
the presence of a catalyst like Ni, Pt or Pd.
Ni or Pt or Pd H 2 + Ni or Pt or Pd
Notes CH ≡ CH + H2 ⎯⎯⎯⎯⎯⎯
573 K
⎯→ CH2 = CH2 ⎯⎯⎯⎯⎯⎯⎯⎯⎯ → CH3 –CH3

(ii) Addition of Halogens : When halogens are added to alkynes, they form
1,2-dihaloalkenes and 1,1,2,2-tetrahaloalkanes.

CH ≡ CH ⎯⎯⎯⎯⎯⎯
Br2 in CCl4 Br2 in CCl4
→ CHBr = CHBr ⎯⎯⎯⎯⎯⎯ → CHBr2 – CHBr2
Ethyne 1,2-Dibromoethene 1,1,2,2-Tetrabromoethane

(iii) Addition of Halogen Acids (HX) : Addition of HBr to ethyne is as

follows :

CH ≡ CH ⎯⎯⎯
HBr HBr
→ CH2 = CHBr ⎯⎯⎯ → CH3 – CHBr2
Ethyne Bromoethene 1,1–Dibromoethane

(iv)Addition of Water : Addition of water takes place in the presence of

mineral acids like H2SO4 and in the presence of Hg2+ as the catalyst.
40% H SO Rearrangement
CH ≡ CH + H2O ⎯⎯⎯⎯⎯⎯
2 4
⎯⎯⎯⎯⎯⎯⎯
→ [CH2 = CHOH] ←⎯⎯⎯⎯⎯⎯ ⎯→ CH CHO
1% HgSO 4 3
Ethyne Vinyl Alcohol Ethanal
(Unstable)

(v) Addition of H2SO4: Conc. H2SO4 adds to ethyne as shown below.

conc. H SO H SO
CH ≡ CH ⎯⎯⎯⎯⎯⎯
2 4 2 4
→ CH2 = CHHSO4 ⎯⎯⎯⎯→ CH3 – CH (HSO4)2
Vinyl hydrogen sulphate Ethylidene hydrogen sulphate

2. Oxidation : Alkynes undergo oxidation with oxygen, KMnO4 and ozone.

(i) Oxidation with KMnO4
COOH
Cold alkaline KMnO 4
CH ≡ CH + 4 [O] ⎯⎯⎯⎯⎯⎯⎯⎯⎯
→
Ethyne COOH
Ethanedioic acid
The colour of alkaline solution of KMnO4 is discharged on reaction with
alkynes. Alkynes on heating with alkaline KMnO4 give carboxylic acids.
KMnO + KOH
R – C ≡ C – R′ ⎯⎯⎯⎯⎯⎯⎯
4
heat
→ RCOOH + R′ COOH

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However, ethyne, on similar treatment, gives carbon dioxide and water. Compounds

KMnO + KOH
CH ≡ CH + 4 [O] ⎯⎯⎯⎯⎯⎯⎯
4
heat
[O]
→ (COOH)2 ⎯⎯⎯
Heat
→ 2 CO2 + H2O

Combustion : Combustion of ethyne in excess of oxygen or air gives carbon

dioxide and water as shown below :
Notes
2 C2H2 + 5 O2 ⎯⎯⎯→ 4 CO2 + 2 H2O ΔH = –1300 KJ
heat
mol–1

Ozonolysis : On ozonolysis, alkynes give dicarbonyl compounds at the

position of C≡C without breaking the chain of carbon atoms as shown below:

+O O Zn / H O
CH ≡ CH ⎯⎯⎯
3→
HC CH ⎯⎯⎯⎯⎯
2 →H–C–C–H

O O O O

3. Formation of Acetylides : Ethyne forms precipitates of copper and silver

acetylides when passed through ammonical solution of cuprous chloride
and ammonical silver nitrate, respectively.

CH ≡ CH + 2Cu(NH3)2 ⎯⎯
→ CuC ≡ CCu + 2 NH+4 + 2 NH3
Cuprous acetylide (red)

CH ≡ CH + 2Ag(NH3)2 ⎯⎯
→ AgC ≡ CAg + 2 NH+4 + 2 NH3
Silver acetylide (white)

24.3.4 Acidic Nature of Ethyne

The acidic nature of hydrocarbons can be determined with the help of the
percentage (%) of s-character of the hydrocarbon. The greater the percentage of
s-character of a hydrocarbon, the more will be its acidic nature.
Table 24.2 : % s-Character of hyrid orbitals in Hydrocarbons
Hydrocarbon Type of hybridization (%) s-character
Alkanes sp3 25%
Alkenes sp2 33.3%
Alkynes sp 50%
As alkynes have 50% s- character, they are the most acidic in nature. An sp-
hybridized carbon atom is more electronegative than sp2 or sp3 carbon atoms.
Due to greater electronegativity of sp hybridized carbon atom in ethyne, hydrogen
atom is less tightly held by the carbon and hence, it can be removed as a proton
(H+) by a strong base like sodium metal and sodamide. The following reactions

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Chemistry of Organic
Compounds of ethyne with sodium and sodamide confirm its acidic nature. In these
reactions, disodium acetylide is formed.
H – C ≡ C – H + 2 Na ⎯⎯⎯
Heat
→ Na – C ≡ C – Na + H2
Ethyne (Acetylene) Disodium Acetylide

H – C ≡ C – H + 2 NaNH2 ⎯⎯⎯
Heat
→ Na – C ≡ C – Na + 2 NH3
Notes Ethyne Sodamide Disodium Acetylide

24.3.5 Uses of Alkynes

Ethyne (acetylene) is used for producing oxyacetylene flame (2800ºC) which is
used for for welding and cutting of iron and steel. It is also used for artificial ripening
of fruits and vegetables. It also finds use in the production of a number of other
organic compounds such as ethanal, ethanoic acid, ethanol, synthetic rubbers and
synthetic fibre orlon.

24.3.6 Distinction Between Alkanes, Alkenes and Alkynes

The folloiwng table shows different tests for distinction between alkanes, alkenes
and alkynes :
Table 24.3 : Tests for identification of alkanes, alkenes and alkynes
S.No Test Alkanes Alkenes Alkynes
1. Add bromine dissolved in No change Reddish brown Reddish brown
carbon tetrachloride. colour of Br2 colour of Br2 is
is discharged discharged

2. Add alkaline solution of No change Purple colour Purple colour of

KMnO4 (Baeyer’s reagent) of KMnO4 is KMnO4 is
discharged discharged

3. Add ammonical solution of No change No change White ppt. of

silver nitrate silver acetylide
is formed

4. Add ammonical solution of No change No change Red ppt. of

cuprous chloride (Cu2Cl2) cuprous acetylide
is formed

INTEXT QUESTIONS 24.3

1. How is ethyne prepared from calcium carbide?
2. Give one reaction to confirm the acidic nature of ethyne.
3. What is the percentage of s-character in ethane, ethene and ethyne?

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24.4 AROMATIC HYDROCARBONS Compounds

Till now, we have explained various methods of preparation of aliphatic

hydrocarbons. Now, we shall deal with an aromatic hydrocarbon (benzene) in
detail. It is one of the major components obtained by the destructive distillation
of coal as shown in Fig. 24.1

COAL Notes
Destructive Distillation

Coke Hot vapour and gases cooled and

(Solid residue) passed through water

Condensed Liquid Coal gas

[Allowed to stand, two layers are formed] [Uncondensed gas]

Ammoniacal liquor Coal tar

(Upper Layer) (Lower Layer)
Fractional Distillation

Crude light oil Middle oil Heavy Oil Green Oil Pitch
(Benzene, (Phenol) (alkyl Phenols (anthracene and (Residue)
Toluene and Naphtholas and Phenanthrene) Mainly carbon
Xylenes) Naphthalene)

Fig. 24.1 : Destructive Distillation of coal

24.4.1 Structure of Benzene

The molecular formula of benzene is C6H6 which indicates that benzene is an
unsaturated hydrocarbon. The unsaturation in benzene can be verified by the
following reactions.
(i) Benzene undergoes the addition of H2 in the presence of Ni or Pt as catalyst.
Ni or Pt
C6H6 + 3H2 ⎯⎯⎯⎯ ⎯ → C6H12
Benzene Cyclohexane

(ii) Benzene undergoes the addition of chlorine in the presence of sunlight.

hν
C6H6 + 3 Cl2 ⎯⎯→ C6H6Cl6
Benzene Benzene hexachloride (B.H.C.)

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Compounds Benzene does not respond to the tests of unsaturation which are shown by alkenes
and alkynes i.e., both the alkenes and the alkynes decolourize bromine water and
alkaline solution of potassium permanganate (Bayer’s Reagent). However, benzene
undergoes substitution reactions.
Fe or FeCl3
e.g. C6H6 + Br2 ⎯⎯⎯⎯⎯⎯ → C6H5Br + HBr
Benzene Bromobenzene
Notes
Kekule Structure : A ring structure for benzene was proposed by Kekule in
1865. According to him, six carbon atoms are joined to each other by alternate
single and double bonds to form a hexagon ring. As the proposed structure of
benzene has three double bonds, so its properties should resemble with the
properties of alkenes. But the chemical properties of benzene are different from
alkenes.
or

As Kekule’s structure contains three single bonds and three double bonds, one
may expect that in benzene there should be two different bond lengths i.e. 154
pm for C-C single bond and 134 pm for C=C double bond. But the experimental
studies show that benzene is regular hexagon with an angle of 1200 and all the
carbon-carbon bond lengths are equal i.e. 139 pm.

If Kekule’s structure is to be taken as a true structure, then benzene should form

only one monosubstitution product and two ortho distubstitution products, shown
below as (a) and (b).
Cl Cl
Cl Cl

(a) (b)
In structure (a), the two halogen atoms are on the doubly bonded carbon atoms,
whereas in structure (b), the two halogen atoms are on singly bonded carbon
atoms. As per the Kekule’s structure these two isomers (a and b) should exist and
show different properties. But, in reality, only one ortho disubstituted product
exists. In order to explain this, Kekule proposed a dynamic equilibrium between
the two structures.
Cl Cl
Cl Cl

Kekule’s structure does not explain the stability of benzene and its some unusual
reactions. Resonance can explain the unusual behaviour of benzene. Let us now
study about resonance.

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Resonance : The phenomenon by virtue of which a single molecule can be Compounds
represented in two or more structures is called resonance. The actual structure
is the resonance hybrid of all the canonical or resonating structure. (see lesson
25)
Heat of hydrogenation data provides proof for resonance stabalization in benzene.
The heat of hydrogenation is the amount of heat liberated when hydrogen
is added to one mole of an unsaturated compound in the presence of a Notes
catalyst.

Catalyst
Cyclohexene + H2 ⎯⎯⎯⎯→
Heat
Cyclohexane + 119.5 KJ mol–1
(One – C = C– bond)

If the three double bonds in benzene do not interact, then it should behave like
cyclohexatriene and the amount of heat liberated on adding there molecules of
hydrogen should be 358.5 KJ mol–1. But, the actual heat of hydrogenation of
benzene is 208.2 kJ mol–1.

Catalyst
Benzene + 3H2 ⎯⎯⎯⎯→
Heat
Cyclohexane + 208.2 kJ mol–1
(Three – C = C– bond)

This difference of (358.5 – 208.2) 150.3 kJ mol–1 in the heat of hydrogenation is

the measure of stability of benzene. Benzene acquires stability due to resonance
and hence, this energy is called resonance energy of benzene.
Thus, the structure of benzene can be described as a resonance hybrid of two
equivalent forms, (I) and (II). None of these two forms is correct by itself.

I II III
Resonance forms of Resonance hybrid
benzene structure showing
delocalisation of electrons

and the actual structure is intermediate of these two forms. This can be represented
as III where the circle inside the ring indicates the equivalence of the carbon-
carbon bonds. The carbon-carbon bond length has been found to be 139 pm.
which is same for all the carbon-carbon bonds in benzene. Also, this value of
bond length is intermediate between the typical C—C single (154 pm) and C=C
double bond (134 pm) lengths.

CHEMISTRY 239
 MODULE - 7 Hydrocarbons
Chemistry of Organic
Compounds Molecular Orbital Picture of Benzene
All the six carbon atoms of benzene are sp2 hybridised. All C—C—C bond angles
are 120° and there is a p orbital on each carbon atom. All the six p-orbitals are
perpendicular to the plane of the six-membered carbon ring. The overlap of these
p orbitals leads to a delocalised electron cloud above and below the place of the
carbon ring. This is shown below in IV and V.
Notes
H H

H H

H H
IV V

24.4.2 Aromaticity
So far you have studied that benzene
z is a cyclic conjugated molecule.

z is unusually stable.
z is planar in nature and its all C — C bond lengths are equal.
z can be represented as a resonance hybrid of two structures.
z undergoes substitution reactions rather than addition reactions.
Though the above properties indicate that benzene is aromatic in nature. But to
complete the argument for its aromatic nature, we have to check whether it follows
Huckel’s rule or not. According to Huckel rule – a molecule is aromatic only if
it has a planar, monocyclic system of conjugated 4n + 2 π electrons where n = 0,
1, 2, 3, …. Thus, molecules with 2, 6, 10, 14 π … electrons can be aromatic.
For example, in Benzene, C6H6
No. of π electrons = 6e– (3π bonds × 2e– = 6e–)
Using formula,
4n + 2 = No. of π electrons Benzene
4n + 2 = 6 gives n = 1
Hence, benzene is aromatic.
Let us take another example, i.e. 1,4-hexadiene
For this compound, No. of π electron = 4e– (2π bond × 2e–)
Using formula,
Hex-1, 4-diene
4n + 2 = No. of π electrons

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Chemistry of Organic
4n + 2 = 4 Compounds

2
n= = 0.5
4
Hence, the value of n is 0.5. So, it does not obey Huckel rule and is non aromatic.

24.4.3 Physical Properties of Aromatic Hydrocarbons

1. Benzene and its homologues are colourless liquids having a characteristic Notes
odour.
2. They are immiscible in water but are miscible in all proportions with organic
solvents such as alcohol, ether, petrol, etc. They dissolve fats and many other
organic substances.
3. Most of the aromatic hydrocarbons are lighter than water.
4. Their boiling points show a gradual increase with increasing molecular mass
e.g. benzene (b.p. 353 K), toluene (b.p. 383 K) and ethylbenzene (b.p. 409
K) and so on.
CH3 C2H5

Benzene Toluene Ethylbenzane

(b.p. 353 K) (b.p. 383 K) (b.p. 409 K)

24.4.4 Chemical Properties of Aromatic Hydrocarbons

Aromatic hydrocarbons generally undergo electrophilic substitution reactions in
which hydrogen atom of the aromatic ring is replaced by an electrophile. Such
reactions are discussed below in detail taking benzene as an example.
(i) Halogenation : The reaction in which a hydrogen atom of benzene is replaced
by a halogen atom is called halogenation of benzene. Halogenation takes place in
the presence of iron, or ferric halides (FeX3, where X = Cl or Br).
X

Fe or FeX3
+ X2 ⎯⎯⎯⎯⎯ ⎯→ + HX
Halobenzene
In case of iodination the HI formed can reduce iodobenzene back to be benzene
which is prevented by carrying out this reaction in the presence of HNO3 or
HIO3. These acids react with HI as soon as it is formed.
I

conc. HNO3
2 + I2 ⎯⎯⎯⎯⎯⎯ → 2

Iodobenzene

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Compounds (ii) Nitration : The chemical reaction in which a hydrogen atom of benzene ring
is replaced by –NO2 group, is called nitration. It is carried out in the presence of
nitrating mixture, i.e. a mixture of conc. HNO3 and conc. H2SO4. Nitronium ion
(NO+2 ) so formed acts as an electrophile.

→ 2 HSO 4− + NO+2 + H3O+

2 H2SO4 + HNO3 ⎯⎯
NO2
Notes
−
+ NO+2 ⎯⎯⎯⎯
HSO4
→ + H2SO4

Nitrobenzene
(iii) Sulphonation : The chemical reaction in which the hydrogen atom of benzene
is replaced by –SO3H group when benzene is heated with fuming sulphuric acid
(oleum), is called sulphonation.
SO3H

+ (H2SO4 + SO3) ⎯⎯
→ + H2O

Fuming sulphuric acid Benzenesulphonic acid

(iv) Friedel–Craft’s Reactions : In Friedel-Craft’s reaction, benzene is heated

either with alkyl halide (alkylation) or acyl halide (acylation) in the presence of
a catalyst (anhydrous AlCl3). The products formed are alkyl or acyl derivatives of
benzene.
Alkylation
CH3

Anhydrous AlCl
+ CH3Cl ⎯⎯⎯⎯⎯⎯⎯
3
→ + HCl
Heat
Benzene Chloromethane Toluene
Acylation
COCH3

Anhydrous AlCl
+ CH3COCl ⎯⎯⎯⎯⎯⎯⎯
3
→ + HCl
Heat
Benzene acetyl chloride Acetophenone

24.4.5 Directive Influence of Functional Groups

In case of substituted aromatic compounds, the functional group(s) already present
directs the next incoming group to a particular position in the aromatic ring.. It is
called directive influence of the group already attached to the benzene ring. For
example, phenol on chlorination gives a mixture of ortho – chlorophenol and
para– chlorophenol as – OH groups is an ortho and para directing group.

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Chemistry of Organic
Compounds
OH OH OH

FeCl Cl
+ Cl2 ⎯⎯⎯ 3
Heat
⎯
→ +
Phenol
o-Chlorophenol
Cl
p-Chlorophenol
Notes
In case of nitrobenzene, we find that –NO2 group is a meta directing group and
hence, the product obtained on chlorination is meta-chloronitrobenzene.

NO2 NO2

FeCl
+ Cl2 ⎯⎯⎯
3
⎯→
Heat Cl
Nitrobenzene m-Chloronitrobenzene

24.4.6 Carcinogenicity & Toxicity

There exist several aromatic compounds-many of them being very important for
the life while there are some others which are harmful. A large number of them
are toxic in nature. For example benzene is carcinogenic in nature.
Another such hydrocarbon, is benzo[α] pyrene which has been found in cigarette
smoke and in the exhaust from automobiles. This compound is also carcinogenic
and can cause skin cancer in mice.

Benzo [a] pyrene

24.4.7 Uses of Aromatic Hydrocarbons

Benzene is used as a solvent for several organic compounds and thus, acts as a
medium for carrying out synthetic reactions. It is the basic aromatic hydrocarbon
and can be converted to other organic compounds by carrying out substitution in
the benzene ring. Toluene, a higher homologue of the benzene, finds its uses for
dry-cleaning, as a solvent, and as a starting material for the manufacture of dyes,
drugs, explosive (trinitrotoluene, T.N.T.), benzaldehyde, benzoic acid etc.

CHEMISTRY 243
 MODULE - 7 Hydrocarbons
Chemistry of Organic
Compounds

INTEXT QUESTIONS 24.4

1. What is the value of resonance energy of benzene?
2. Name the product formed when :
(i) benzene reacts with chlorine in the presence of light.
Notes
(ii) phenol reacts with chlorine in the presence of FeCl3.
(iii) nitrobenzene reacts with chlorine in the presence of FeCl3.
3. Classify the following into o-and p- or m-directing groups :
–NH2, –NO2, –Cl, –C–R , –OH, –SO3H
O

WHAT YOU HAVE LEARNT

z Alkanes can be prepared by (i) the reduction of haloalkanes, (ii) action of
water or alcohol on Grignard’s reagent, (iii) Wurtz reaction and (iv)
hydrogenation of unsaturated hydrocarbons.
z Physical properties of hydrocarbons depend on the intermolecular forces of
attraction. which in turn depend upon the shapes of molecules and their surface
area.
z The melting points of hydrocarbons depends upon the symmetry of the
molecules i.e. hydrocarbons with even number of carbon atoms are more
symmetrical and have higher melting points.
z Rotation about carbon-carbon single bond leads to various conformations of
a molecule. Ethane has many conformations out of which the staggered
conformation is the most stable one and the eclipsed conformation is the
least stable one.
z Alkenes can be prepared by dehydrohalogenation of alkyl halides and by
dehydration of alcohols.
z Alkenes and alkynes undergo addition reactions e.g. addition of hydrogen,
halogens, halogen acids, water, sulphuric acid etc. due to the presence of
carbon-carbon double or triple bonds.
z Addition of halogen acids and other unsymmetrical reagents to unsymmetrical
alkenes and alkynes takes place according to the Markownikoff’s rule.
z Alkenes undergo polymerization on heating under pressure.

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z All hydrocarbons (saturated as well as unsaturated) form CO2 and H2O on Compounds
combustion and liberate energy.
z An alkaline solution of KMnO4 can oxidize alkenes and alkynes forming
different products such as carboxylic acids, aldehydes and/or ketones and
carbon dioxide.
z Ozone can oxidize unsaturated hydrocarbons (alkenes and alkynes) forming
ozonides which when further reacted with water in the presence of zinc dust Notes
either form aldehydes or ketones or both.
z Reaction of ozone with alkenes can be used to determine the position of
double bond.
z Ethyne can be prepared by the action of water on calcium carbide and by
dehydrogenation of dihaloalkanes.
z Alkynes are acidic in nature due to sp-hybridization of carbon atoms. Because
sp hybridized carbon atoms are more electronegative than sp2 and sp3, and
the bond between C—H is weakened. Hence, hydrogen atoms in alkynes can
be replaced by certain metal atoms.
z Alkanes, alkenes and alkynes can be distinguished by using:
a) Br2 dissolved in carbon tetrachloride.
b) Ammoniacal solution of AgNO3
c) Ammoniacal solution of Cu2Cl2
d) Alkaline solution of KMnO4
z Benzene is obtained by destructive distillation of coal.
z A ring structure of benzene was suggested by Kekule. Actual structure of
benzene is the resonance hybrid of the canonical structures.
z Aromatic hydrocarbons undergo substitution reactions i.e. the reactions in
which hydrogen atom of hydrocarbons is replaced by another atom or group
of atoms. Halogenation, sulphonation, nitration and Friedel Craft’s reaction
are substitution reactions of benzene.
z The position of second substituent on a benzene ring depends upon the nature
of the group already present.

TERMINAL EXERCISE
1. What happens when : (Write chemical equations)
(i) Iodoethane is heated with HI in the presence of red phosphorus.
(ii) 2-Chlorobutane reacts with sodium metal.

CHEMISTRY 245
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Chemistry of Organic
Compounds (iii) Ethyl magnesium bromide is reacted with methyl alcohol (methanol).
(iv) 2-Chloropropane reacts with alcoholic solution of KOH.
(v) 1,1-Dichloroethane reacts with alcoholic solution of KOH.
2. Give reasons for the following :
(i) The boiling point of neopentane is less than that of n-pentane.
Notes (ii) Stability of benzene ring
(iii) Boiling points of hydrocarbons decrease with the increase in branching.
3. How will you prepare the following?
(i) Ethane from ethene
(ii) Ethene from ethanol
(iii) Cyclohexane from benzene
(iv) Methane from sodium acetate
(v) Butane from bromoethane
4. What happens when (write balanced chemical equations):
(i) Hydrochloric acid is added to ethene.
(ii) Hydrobromic acid (HBr) is added to propene in the presence of
benzoyl peroxide.
(iii) Benzene reacts with chloromethane in the presence of anhydrousAlCl3.
(iv) Br2 is added to ethyne.
(v) Methane is oxidized with oxygen in the presence of copper at 475K
and a high pressure of 120 atm.
5. How are the following conversions carried out?
(i) Ethyne to ethane
(ii) Benzene to nitrobenzene
(iii) Ethyl alcohol (ethanol) to ethene
(iv) Ethyne to ethanedioic acid
(v) Benzene to o-nitrochlorobenzene.
6. You are provided with three gas jars containing ethane, ethene and ethyne.
Give the suitable chemical tests to identify the three hydrocarbons.
7. What is ozonolysis? How is it used to determine the position of a double
bond?
8. Give reasons for the following :
(i) Alkanes do not undergo addition reactions like alkenes and alkynes.
(ii) Ethyne is more acidic than ethane.

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(iii) Ethene undergoes polymerization but not ethane. Compounds
(iv) Benzene undergoes electrophilic substitution reactions.

ANSWERS TO INTEXT QUESTIONS

Notes
24.1
1. They are used as fuels and to prepare detergents, dyes, drugs, explosives etc.
Hydrocarbons are used to prepare some important organic compounds like
alcohols, aldehydes, carboxylic acids etc.
2. The alkyl magnesium halides (R-MgX) are called Grignard’s reagent.
3. Easily replaceable hydrogen present in a molecule is called active hydrogen.
4. The physical properties of hydrocarbons differ from one another due to
difference in molecular mass, surface area, intermolecular force of attraction.
5. Methane and ethane are gases, pentane and hexane are liquids.
6. Three isomers of pentane are : n-pentane, isopentane and neopentane.
7. n-pentane has higher boiling point than n-butane.

8. C3H8 + 5 O2 ⎯⎯
→ 3 CO2 + 4 H2O

24.2
1. Trans-2-butene has higher boiling point than cis-isomer.
2. Ethane-1, 2-diol
3. Hydrogen in presence of catalist Ni, Pt or Pd
4. Epoxyethane is produced.

24.3
1. Calcium carbide is reacted with water to prepare ethyne.
CaC2 + 2H2O ⎯→ C2H2 + Ca(OH)2
2. Reaction with sodium metal confirms the acidic nature of ethyne.
H — C ≡ C — H + 2 Na ⎯→ Na — C ≡ C — Na + H2
Ethyne Disodium acetylide

3. The s-character in : Ethane = 25%,

Ethene = 33%,
Ethyne = 50%

CHEMISTRY 247
 MODULE - 7 Hydrocarbons
Chemistry of Organic
Compounds 24.4
1. The resonance energy of benzene is 150.3 KJ mol–1.
2. (i) Benzene hexachloride (BHC).
(ii) o-Chlorophenol and p-chlorophenol.
(iii) m-Chloronitrobenzene.
Notes
3. o – and p – directing groups : –NH2, –Cl, – OH
m-directing groups : NO2, –C–R , – SO3H
O

248 CHEMISTRY