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Unit 13

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Hydrocarbons

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(Concepts, Questions & Exceptions)
Introduction:
1. The Hydrocarbon are compounds of carbon and hydrogen only.

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2. All these fuels contain mixture of hydrocarbons, which are sources of energy.
3. LPG (liquified petroleum gas) whereas CNG (compressed natural gas).
4. Petrol, diesel and kerosene oil are obtained by the fractional distillation of petroleum found

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under the earth’s crust.
5. Coal gas is obtained by the destructive distillation of coal.
6. Automobiles need fuels like petrol, diesel and CNG.

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7. Hydrocarbons are also used for the manufacture of polymers like polythene, polypropene,

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polystyrene etc.
8. Higher hydrocarbons are used as solvents for paints.
9. They are also used as the starting materials for manufacture of many dyes and drugs.

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Classification:
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ALKANES
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1. Alkanes are saturated open chain hydrocarbons containing carbon-carbon single bonds.
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2. Methane (CH� ) is the first member of this family. Methane is a gas found in coal mines and
marshy places. This hydrocarbon with molecular formula C� H� is known as ethane.
3. Thus you can consider C� H� as derived from CH� by replacing one hydrogen atom by
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−CH� group.
4. The next molecules will be C� H� , C� H�� …
 These hydrocarbons are inert under normal conditions as they do not react with acids, bases and
other reagents. Hence, they were earlier known as paraffins (little affinity).
The general formula for alkanes is Cn H�n��

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Bong Angle: H-C-H bond angles are of 109.5°
Bond length: C-C and C-H bond lengths are 154
pm and 112 pm

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Hybridization: sp3

Types of bonds: C–C and C–H σ bonds

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Nomenclature and Isomerism: They show Chain isomers

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Such structural isomers which differ in chain of carbon atoms are known as chain isomers.

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C� H�� , C� H�� , C� H��

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C� H�� has got five isomers and C� H�� has nine. As many as 75 isomers are possible for C�� H��
Based upon the number of carbon atoms attached to a carbon atom, the carbon atom is termed as
primary (1°), secondary (2°), tertiary (3°) or quaternary (4°).
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a) Carbon atom attached to one carbon atoms is known as primary

b) Carbon atom attached to two carbon atoms is known as secondary.
c) Tertiary carbon is attached to three carbon atoms
d) Neo or quaternary carbon is attached to four carbon atoms.
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 Preparation:
1. From unsaturated hydrocarbons: Reduction (hydrogenation)

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a) Dihydrogen gas adds to alkenes and alkynes in the presence of finely divided catalysts
like platinum, palladium or nickel to form alkanes.

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b) This process is called hydrogenation.
c) These metals adsorb dihydrogen gas on their surfaces and activate the hydrogen-
hydrogen bond.

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d) Platinum and palladium catalyse the reaction at room temperature but relatively higher
temperature and pressure are required with nickel catalysts

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2. From alkyl halides:
a) Alkyl halides (except fluorides) on reduction with zinc and dilute hydrochloric acid

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give alkanes
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b) Alkyl halides on treatment with sodium metal in dry ethereal (free from moisture) solution
give higher alkanes.
c) This reaction is known as Wurtz reaction and is used for the preparation of higher alkanes
containing even number of carbon atoms.
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Q. Why is Wurtz reaction not preferred for the preparation of alkanes containing odd number of
carbon atoms? Illustrate your answer by taking one example
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Q. Which of the following alkanes can be synthesized by the wurtz reaction in a good yield?
(A) (CH3)2–CH–CH2–CH(CH3)2 (B) (CH3)2CH–CH2–CH2–CH(CH3)2
(C) CH3–CH2 (CH3)2CH2–CH3 (D) (CH3)3C–CH2–CH2–CH3
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3. From carboxylic acids:

i) Sodium salts of carboxylic acids on heating with soda lime (mixture of sodium hydroxide and
calcium oxide) give alkanes containing one carbon atom less than the carboxylic acid.
This process of elimination of carbon dioxide from a carboxylic acid is known as decarboxylation
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ii) Kolbe’s electrolytic method: An aqueous solution of sodium or potassium salt of a carboxylic
acid on electrolysis gives alkane

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Methane cannot be prepared by this method. Why?

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Physical properties:
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1. Alkanes are almost non-polar molecules because of the covalent nature of C-C and C-H
bonds and due to very little difference of electronegativity between carbon and hydrogen
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atoms.
2. They possess weak van der Waals forces.
3. Due to the weak forces, the first four members, C� to C� are gases, C� to C�� are liquids and
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those containing 18 carbon atoms or more are solids at 298 K.

4. They are colourless and odourless.
5. It is generally observed that in relation to solubility of substances in solvents, polar
substances are soluble in polar solvents, whereas the non-polar ones in non-polar solvents
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i.e., like dissolves like

Boiling point (b.p.):
1. Steady increase in boiling point with increase in molecular mass.
2. This is due to the fact that the intermolecular van der Waals forces increase with increase
of the molecular size or the surface area of the molecule.
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3. With increase in number of branched chains, boiling point decrease

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Q. What effect does branching of an alkane chain has on its boiling point?

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Q. The compound with the highest boiling point is
(a) n-Hexane (b) n-Pentane (c) 2, 2-dimethyl propane (d) 2-methyl butane

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Chemical properties:
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As already mentioned, alkanes are generally inert towards acids, bases, oxidising and reducing
agents.
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1. Substitution reactions: One or more hydrogen atoms of alkanes can be replaced by halogens,
nitro group and sulphonic acid group.
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Halogenation takes place either at higher temperature (573-773 K) or in the presence of diffused
sunlight or ultraviolet light.
Lower alkanes do not undergo nitration and sulphonation reactions.
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a) It is found that the rate of reaction of alkanes with halogens is F� > Cl� > Br� > I�
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b) Rate of replacement of hydrogens of alkanes is: 3° > 2° > 1°.

c) Fluorination is too violent to be controlled.
d) Iodination is very slow and a reversible reaction. It can be carried out in the presence of
oxidizing agents like HIO� or HNO� .
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Q. Direct iodination of methane is not practicable because

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(A) Iodine–iodine bond is easily broken
(B) HI formed in the reaction reduces CH3 to CH4
(C) CH3I is unstable

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(D) CH3 is formed with difficulty
Q. Order of rate of reaction of ethane with halogens is

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(a) I > Br > Cl > F (b) Cl > I > Br > F (c) Cl > Br > F > I (d) F > Cl > Br > I

Mechanism: Halogenation is supposed to proceed via free radical chain mechanism involving
three steps namely initiation, propagation and termination

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(i) Initiation: The reaction is initiated by homolysis of chlorine molecule in the presence
of light or heat. The Cl–Cl bond is weaker than the C–C and C–H bond and hence, is
easiest to break

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(ii) Propagation:
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Repeat steps (a) and (b) respectively and thereby setup a chain of reactions
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(iii)Termination:
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2. Combustion: Alkanes on heating in the presence of air or dioxygen are completely

oxidized to carbon dioxide and water with the evolution of large amount of heat
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Q. Write chemical equations for combustion reaction of the following hydrocarbons:

(i) Butane
(ii) Pentene
(iii) Hexyne
(iv) Toluene
 Due to the evolution of large amount of heat during combustion, alkanes are used as fuels.
During incomplete combustion of alkanes with insufficient amount of air or dioxygen, carbon
black is formed which is used in the manufacture of ink, printer ink, black pigments and as

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filters

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3. Controlled oxidation: Alkanes on heating with a regulated supply of dioxygen or air
at high pressure and in the presence of suitable catalysts give a variety of oxidation products

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iv) Ordinarily alkanes resist oxidation but alkanes having tertiary H atom can be oxidized to
corresponding alcohols by potassium permanganate

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4. Isomerisation:
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5. Aromatization: dehydrogenated and cyclised to benzene and its homologues. This reaction
is known as aromatization or reforming.
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Toluene (C� H� ) is methyl derivative of benzene. Which alkane do you suggest for reparation of
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toluene ?
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Q. The product obtained on heating n-heptane with Cr2O3-Al2O3 at 600 ºC is -

(A) cyclohexane (B) cyclohexene (C) benzene (D) toluene
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6. Reaction with steam: This method is used for industrial preparation of dihydrogen gas
 7. Pyrolysis: Higher alkanes on heating to higher temperature decompose into lower alkanes,
alkenes etc. is called pyrolysis or cracking

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Pyrolysis of alkanes is believed to be a free radical reaction. Preparation of oil gas or petrol gas

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from kerosene oil or petrol involves the principle of pyrolysis.

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Conformations

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1. This free rotation about C–C single bond results into different spatial arrangements of

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atoms in space which can change into one another.

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2. Such spatial arrangements of atoms which can be converted into one another by rotation
around a C-C single bond are called conformations or conformers or rotamers.
3. Alkanes can thus have infinite number of conformations by rotation around C-C single
bonds
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4. Rotation around a C-C single bond is not completely free.
5. It is hindered by a small energy barrier of 1-20 kJ mol−� due to weak repulsive interaction
between the adjacent bonds.
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6. Such a type of repulsive interaction is called torsional strain

Conformations of ethane:
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1. This rotation around the C-C axis results into infinite number of spatial arrangements of
hydrogen atoms attached to one carbon atom with respect to the hydrogen atoms attached
to the other carbon atom.
2. Thus there are infinite number of conformations of ethane.
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3. There are two extreme cases. One such conformation in which hydrogen atoms attached to
two carbons are as closed together as possible is called eclipsed conformation and the
other in which hydrogens are as far apart as possible is known as the staggered
conformation.
4. Any other intermediate conformation is called a skew conformation.
5. In all the conformations, the bond angles and the bond lengths remain the same.
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6. Eclipsed and the staggered conformations can be represented by Sawhorse and Newman
projections.
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Relative stability of conformations:
1. Staggered form of ethane, the electron clouds of carbon-hydrogen bonds are as far apart
as possible. Thus, there are minimum repulsive forces, minimum energy and maximum

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stability of the molecule.

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2. In the eclipsed form, the electron clouds of the carbon-hydrogen bonds come closer to
each other resulting in increase in electron cloud repulsions, molecule will have to possess
more energy and thus has lesser stability.
3. The repulsive interaction between the electron clouds, which affects stability of a

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conformation, is called torsional strain.
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4. Magnitude of torsional strain depends upon the angle of rotation about C–C bond. This
angle is also called dihedral angle or torsional angle
5. Of all the conformations of ethane, the staggered form has the least torsional strain and the
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eclipsed form, the maximum torsional strain.

6. The energy difference between the two extreme forms is of the order of 12.5 kJ mol−� ,
which is very small. Even at ordinary temperatures it can be overcome through collision
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7. It has not been possible to separate and isolate different conformational isomers of ethane

Q. Find the correct order for relative energies of the ethane conformations
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(a) staggered < skewed < eclipsed (b) skewed < staggered < eclipsed
(c) skewed < eclipsed < staggered (d) staggered < eclipsed < skewed

Q. The energy difference between staggered and eclipsed conformations of ethane is about -
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(A) 25 kJ/mole (B) 30 kJ/mole (C) 100 kJ/mole (D) 12.5 kJ/mole
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 ALKENES
Alkenes are unsaturated hydrocarbons containing at least one double bond.

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The general formula for alkenes is Cn H�n

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Alkenes are also known as olefins (oil forming) since the first member, ethylene or ethene (C� H�)
was found to form an oily liquid on reaction with chlorine

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Structure of Double Bond:

C=C bond length (134 pm), pi (π) bond 284 kJ mol−�

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C–C single bond (154 pm), sigma (σ) bond 397 kJ mol−�

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Strength of the double bond (bond enthalpy, 681 kJ mol−� ) is greater than that of a carbon-carbon
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single bond in ethane (bond enthalpy, 348 kJ mol−�).

Isomerism: Alkenes show both structural isomerism and geometrical isomerism

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Geometrical isomerism: The restricted rotation of atoms or groups around the doubly bonded
carbon atoms gives rise to different geometries of such compounds. The stereoisomers of this type
are called geometrical isomers.
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Cis isomer Trans isomer

Due to different arrangement of atoms or groups in space, these isomers differ in their properties
like melting point, boiling point, dipole moment, solubility etc.
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Q. Draw cis and trans isomers of the following compounds. Also write their IUPAC names
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Q. Which of the following compounds will show cis-trans isomerism?

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Q. Draw the cis and trans structures of hex-2-ene. Which isomer will have higher b.p. and why?
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Preparation:
1. From alkynes: Partially deactivated palladised charcoal is known as Lindlar’s catalyst.
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Alkenes thus obtained are having cis geometry. Alkynes on reduction with sodium in liquid
ammonia form trans alkenes
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Q. 2-hexyne can be converted into trans-2-hexene by the action of

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(A) H2 – Pd-BaSO4 (B) Li in liq. NH3 (C) H2 – PtO2 (D) NaBH4

2. From alkyl halides: Alkyl halides (R-X) on heating with alcoholic potash eliminate one
molecule of halogen acid to form alkenes.

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This reaction is known as dehydrohalogenation
This is example of β-elimination reaction, since hydrogen atom is eliminated from the β carbon

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atom (carbon atom next to the carbon to which halogen is attached).

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The rate is: iodine > bromine > chlorine, while for alkyl groups it is: tert > secondary > primary

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3. From vicinal dihalides: Vicinal dihalides on treatment with zinc metal lose a molecule of ZnX�
to form an alkene. This reaction is known as dehalogenation
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4. From alcohols by acidic dehydration:

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1. Using concentrated sulphuric acid

2. Elimination of one water molecule (Elimination or acidic dehydration of alcohols)
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Physical properties:
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1. The first three members are gases, the next fourteen are liquids and the higher ones are
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solids.
2. Insoluble in water but fairly soluble in non-polar solvents like benzene, petroleum ether.
3. They show a regular increase in boiling point with increase in size i.e., every -CH� group
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added increases boiling point by 20-30 K.

4. Like alkanes, straight chain alkenes have higher boiling point than isomeric branched chain
compounds
 Chemical properties:
1. Electrophiles addition reactions

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2. Free radical addition reactions
3. Free radical substitution reactions (under special conditions)

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4. Oxidation and ozonolysis reactions
1. Addition of dihydrogen:

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Q. Write structures of all the alkenes which on hydrogenation give 2-methylbutane

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2. Addition of halogens:

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The reddish orange colour of bromine solution in carbon tetrachloride is discharged when bromine
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adds up to an unsaturation site. This reaction is used as a test for unsaturation.
3. Addition of hydrogen halides:
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The order of reactivity of the hydrogen halides is HI > HBr > HCl
a) Addition reaction of HBr to symmetrical alkenes:
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Addition reaction of HBr to unsymmetrical alkenes (Markovnikov Rule):

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Markovnikov rule: The negative part of the addendum (adding molecule) gets attached to that
carbon atom which possesses lesser number of hydrogen atoms
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 Mechanism: reactions proceed through carbocation mediated

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Anti Markovnikov addition or peroxide effect or Kharash effect: In the presence of peroxide,
addition of HBr to unsymmetrical alkenes like propene takes place contrary to the Markovnikov

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rule. This happens only with HBr but not with HCl and HI.

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Mechanism: Peroxide effect proceeds via free radical chain mechanism

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Q. Write IUPAC names of the products obtained by addition reactions of HBr to hex-1-ene
(i) In the absence of peroxide
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(ii) In the presence of peroxide.

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Peroxide effect is not observed in addition of HCl and HI. This may be due to the fact that the H–
Cl bond being stronger (430.5 kJ mol−� ) than H–Br bond (363.7 kJ mol−� ), is not cleaved by the
free radical, whereas the H–I bond is weaker (296.8 kJ mol−�) and iodine free radicals combine
to form iodine molecules instead of adding to the double bond.
Q. Anti-Markownikoff’s addition of HBr is not observed in
(A) Propene (B) But-2-ene (C) Butene (D) Pent-2-ene
 Q. CH3–CH–CH=CH2 + HBr (product) which is predominate; X is
CH3
Br

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(A) CH3–CH–CH=CH2 + HBr (B) CH3–C–CH2 –CH3 (C) CH3–CH–CH–CH3 (D) None is correct

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CH3 CH3 CH3 Br

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4. Addition of sulphuric acid: accordance with Markovnikov rule to form alkyl hydrogen
sulphate by the electrophilic addition reaction.

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5. Addition of water: alkenes react with water to form alcohols, in accordance with the

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Markovnikov rule

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6. Oxidation: (a) Alkenes on reaction with cold, dilute, aqueous solution of potassium
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permanganate (Baeyer’s reagent) produce vicinal glycols. Decolorisation of KMnO� solution is

used as a test for unsaturation
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Q. What would be the product when ethene is oxidised with cold dil. KMnO4 solution
(A) CH2–CH2 (B) H – C – H (C) H – C – OH (D) CO2 + H2O
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OH OH O O

(b) Acidic potassium permanganate or acidic potassium dichromate oxidises alkenes to ketones
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and/or acids depending upon the nature of the alkene and the experimental conditions
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Q. An alkyne C7H12 on reaction with hot alk. KMnO4 and subsequent acidification with HCl yields
a mixture of
CH3– CHCOOH + CH3CH2COOH The alkyne is
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CH3
(A) 3-Hexyne (B)2-Methyl-3-hexyne (C) 2-Methyl-2-hexyne (D)2-Methyl-2-hexene
 7. Ozonolysis: Ozonolysis of alkenes involves the addition of ozone molecule to alkene to form
ozonide, and then cleavage of the ozonide by Zn − H� O to smaller molecules. This reaction is
highly useful in detecting the position of the double bond in alkenes or other unsaturated

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compounds.

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Q. Propanal and pentan-3-one are the ozonolysis products of an alkene? What is the structural

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formula of the alkene?

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Q. An alkene ‘A’ on ozonolysis gives a mixture of ethanal and pentan-3-one. Write structure and
IUPAC name of ‘A’.

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Q. An alkene ‘A’ contains three C – C, eight C – H σ bonds and one C – C π bond. ‘A’ on
ozonolysis gives two moles of an aldehyde of molar mass 44 u. Write IUPAC name of ‘A’.
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Q. Write IUPAC names of the products obtained by the ozonolysis of the following compounds
(i) Pent-2-ene (ii) 3,4-Dimethylhept-3-ene (iii) 2-Ethylbut-1-ene (iv) 1-Phenylbut-1-ene
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8. Polymerisation: Polythene is obtained by the combination of large number of ethene

molecules at high temperature, high pressure and in the presence of a catalyst.

Polypropene is used for the manufacture of milk crates, plastic buckets and other moulded articles.
 ALKYNES
Alkynes are unsaturated hydrocarbons containing at least one triple bond.

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The general formula for alkenes is Cn H�n−�

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The first stable member of alkyne series is ethyne which is popularly known as acetylene.
Acetylene is used for arc welding purposes in the form of oxyacetylene flame obtained by mixing

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acetylene with oxygen gas

Nomenclature and Isomerism:

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Since these two compounds differ in their structures due to the position of the triple bond, they are
known as position isomers

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Structures I and II are position isomers and structures I and III or II and III are chain isomers

Structure of Triple Bond:

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H-C-C bond angle is of 180°

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The strength of C≡C bond (bond enthalpy 823 kJ mol-1) is more than those of C=C bond (bond
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enthalpy 681 kJ mol–1) and C–C bond (bond enthalpy 348 kJ mol–1).
The C≡C bond length is shorter (120 pm) than those of C=C (133 pm) and C–C (154 pm).
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Electron cloud between two carbon atoms is cylindrically symmetrical about the internuclear axis.
Thus, ethyne is a linear molecule.

Preparation: 1. From calcium carbide: Industrial scale

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2. From vicinal dihalides: Vicinal dihalides on treatment with alcoholic potassium hydroxide

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undergo dehydrohalogenation

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Physical properties:

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1. First three members are gases, the next eight are liquids and the higher ones are solids.
2. All alkynes are colourless. Ethyene has characteristic odour. Other members are odourless.
3. Alkynes are weakly polar in nature.
4. They are lighter than water and immiscible with water but soluble in organic solvents like

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ethers, carbon tetrachloride and benzene.
5. Their melting point, boiling point and density increase with increase in molar mass

Chemical properties: Alkynes show acidic nature, addition reactions and polymerization
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1. Acidic character of alkyne:

a) Sodium metal and sodamide (NaNH� ) are strong bases.
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b) With Strong base they react with ethyne to form sodium acetylide with the liberation
of dihydrogen gas.
c) These reactions have not been observed in case of ethene and ethane
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These reactions are not shown by alkenes and alkanes, hence used for distinction between alkynes,
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alkenes and alkanes.

Q. Acidic hydrogen is present in
(A) ethyne (B) ethene (C) benzene (D) ethane
Q. What about the above reactions with but-1-yne and but-2-yne ?
 Q. Which of the following will not react with an ammonical silver nitrate solution
(A) CH3C  CH (B) (CH3)2CH – C  H (C) CH3C  CCH3 (D) HC  CH

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Acidic Character order

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B. Addition reactions: Electrophilic addition reactions

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Addition in unsymmetrical alkynes takes place according to Markovnikov rule

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(i) Addition of dihydrogen:

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(ii) Addition of halogens:
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a) Reddish orange colour of the solution of bromine in carbon tetrachloride is decolourised.

b) This is used as a test for unsaturation.
(iii) Addition of hydrogen halides:
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(iv) Addition of water: one molecule of water adds to alkynes on warming with mercuric
sulphate and dilute sulphuric acid at 333 K to form carbonyl compounds
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C  CH
Q. Hydration of in presence of H2SO4 / HgSO4 gives (as a major product)

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OH
C = CH2 CH= CH COCH3 CH2CHO
(A) (B) (C) (D)
OH 3

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Q. A hydrocarbon (X) of molecular formula C4H6 decolorizes a solution of bromine in carbon

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tetrachloride and gives a white precipitate with ammoniacal silver nitrate solution. The
hydrocarbon (X) on treatment with aqueous H2SO4 containing HgSO4 yields 2-butanone. The
hydrocarbon (X) is

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(A) 1,3-butadiene (B) Cyclobutene (C) 1-butyne (D) 2-butyne
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Polymerisation: (a) Linear polymerisation: linear polymerisation of ethyne takes place to

produce polyacetylene or polyethyne which is a high molecular weight polyene containing
repeating units of (CH = CH – CH = CH ) and can be represented as —(CH = CH – CH = CH)n—
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Thin film of polyacetylene can be used as electrodes in batteries. These films are good conductors,
lighter and cheaper than the metal conductors
(b) Cyclic polymerisation:
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 AROMATIC HYDROCARBON (Benzene)
These hydrocarbons are also known as ‘arenes’.

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Since most of them possess pleasant odour the class of compounds was named as ‘aromatic

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compounds’. Most of such compounds were found to contain benzene ring.
Aromatic compounds containing benzene ring are known as benzenoids and those not containing
a benzene ring are known as non-benzenoids. Some examples of arenes are given below:

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Nomenclature and Isomerism:

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All six hydrogen atoms in benzene are equivalent; so it forms one and only one type of
monosubstituted product.

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When two hydrogen atoms in benzene are replaced by two similar or different monovalent atoms
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or groups, three different position isomers are possible. The 1, 2 or 1, 6 is known as the ortho (o-
), the 1, 3 or 1, 5 as meta (m-) and the 1, 4 as para (p-) disubstituted compounds.
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Structure of Benzene
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1. Benzene was found to be a stable molecule

2. It form a triozonide which indicates the presence of three double bonds.
3. It produce one and only one monosubstituted derivative which indicated that all the six
carbon and six hydrogen atoms of benzene are identical.
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Kekulé in 1865 proposed the following structure for benzene:

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Kekulé structure of benzene fails to explain unusual stability and preference to substitution
reactions than addition reactions
 Q. Write down the products of ozonolysis of 1,2-dimethylbenzene (o-xylene). How does the result
support Kekulé structure for benzene?

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Resonance and stability of benzene:

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1. Benzene is a hybrid of various resonating structures.
2. The two structures, A and B given by Kekulé are the main contributing structures.
3. The hybrid structure is represented by inserting a circle or a dotted circle in the hexagon as

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shown in (C).
4. The circle represents the six electrons which are delocalised between the six carbon atoms
of the benzene ring
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There is equal probability for the p orbital of each carbon atom to overlap with the p orbitals of
adjacent carbon atoms, this can be represented in the form of two doughtnuts (rings) of electron
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clouds, one above and one below the plane of the hexagonal ring as shown below
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Benzene is a planar molecule, all the six C-C bond lengths are of the same order (139 pm) which
is intermediate between C-C single bond (154 pm) and C=C double bond (133 pm). Thus the
 absence of pure double bond in benzene accounts for the reluctance of benzene to show addition
reactions under normal conditions, thus explaining the unusual behaviour of benzene.
Q. Why is benzene extra ordinarily stable though it contains three double bonds?

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Q. Which of the following statement is incorrect

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(a) Benzene undergoes electrophiilic substitution reaction

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(b) Benzene is aromatic
(c) Benzene is stablised by resonance

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(d) Benzene decolourise Br2 water

Aromaticity: To show aromatic character molecule must have

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(i) Planarity

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(ii) Complete delocalisation of the π electrons in the ring
(iii) Must follow Hückel Rule, presence of (4n + 2) π electrons in the ring where n is an
integer (n = 0, 1, 2, . ).

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Q. What are the necessary conditions for any system to be aromatic?

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Q. Explain why the following systems are not aromatic?

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Preparation of Benzene:
1. Cyclic polymerisation of ethyne (already discussed)
2. Decarboxylation of aromatic acids:
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3. Reduction of phenol:
 Q. How would you convert the following compounds into benzene?
(i) Ethyne (ii) Ethene (iii) Hexane

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Physical properties:
1. Aromatic hydrocarbons are non-polar molecules and are usually colourless liquids or solids

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with a characteristic aroma.
2. Naphthalene balls which are used in toilets and for preservation of clothes because of
unique smell of the compound and the moth repellent property.
3. Aromatic hydrocarbons are immiscible with water but are readily miscible with organic

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solvents.

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4. They burn with sooty flame

Chemical properties: Arenes are characterised by electrophilic substitution reactions.

However, under special conditions they can also undergo addition and oxidation reactions

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Electrophilic substitution reactions: The common electrophilic substitution reactions of arenes
are nitration, halogenation, sulphonation, Friedel Craft’s alkylation and acylation reactions in
which attacking reagent is an electrophile (E � )
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(i) Nitration: concentrated nitric acid and concentrated sulphuric acid (nitrating mixture)
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(ii) Halogenation: a Lewis acid like anhydrous FeCl� , FeBr� or AlCl�

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(iv) Sulphonation: oleum

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 (iv) Friedel-Crafts alkylation reaction:

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Q. Why do we get isopropyl benzene on treating benzene with 1-chloropropane instead of n-propyl
benzene

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 P, P is :
CH 3 – CH CH 2


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H3PO4
Q.
CH3
CH3
H3C CH3

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(A) (B) (C) No reaction (D)

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Q. Suggest the name of a Lewis acid other than anhydrous aluminium chloride which can be used

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during ethylation of benzene
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Q. Why does benzene undergo electrophilic substitution reactions easily and nucleophilic
substitutions with difficulty?
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(v) Friedel-Crafts acylation reaction:

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If excess of electrophilic reagent is used, further substitution reaction may take place in which
other hydrogen atoms of benzene ring may also be successively replaced by the electrophile.
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Mechanism of electrophilic substitution reactions:

(a) Generation of the eletrophile
(b) Formation of carbocation intermediate
(c) Removal of proton from the carbocation intermediate
 (a) Generation of the eletrophile: During chlorination, alkylation and acylation of benzene,
anhydrous AlCl3, being a Lewis acid helps in generation of the elctrophile, Cl� , R� , RCO�
(acylium ion) respectively by combining with the attacking reagent

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In the case of nitration:

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In the process of generation of nitronium ion, sulphuric acid serves as an acid and nitric acid as a
base. Thus, it is a simple acid-base equilibrium
Q. Nitrobenzene can be prepared from benzene by using a mixture of conc. HNO3 and conc.

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H2SO4. In the nitrating mixture HNO3 acts as a
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(A) base (B) acid (C) reducing agent (D) catalyst
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b) Formation of Carbocation (arenium ion): Attack of electrophile results in the formation of

σ-complex or arenium ion in which one of the carbon is sp 3 hybridised.
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Sigma complex or arenium ion loses its aromatic character because delocalisation of electrons
stops at sp3 hybridised carbon.
c) Removal of proton:
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Addition reactions: Under vigorous conditions, i.e., at high temperature and/ or pressure in the
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presence of nickel catalyst, hydrogenation of benzene gives cyclohexane

 Under ultra-violet light, three chlorine molecules add to benzene to produce benzene hexachloride,
C� H� Cl� which is also called gammaxane.

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Combustion:

Directive influence of a functional group in monosubstituted benzene:

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Ortho and para directing groups:
1. The groups which direct the incoming group to ortho and para positions are called ortho
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and para directing groups.

2. They increase electron density of benzene ring
3. They activate benzene ring towards ESR
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4. Examples of are –OH, –NH� , –NHR, –NHCOCH� , –OCH�, –CH� , –C� H� , etc.
5. Halogens (-x) are o- and p- directing but they deactivate benzene ring because of their
strong – I effect
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Meta directing group:

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1. The groups which direct the incoming group to meta positions are called meta directing
groups.
2. They decrease electron density of benzene ring
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3. They dactivate benzene ring towards ESR

4. Examples are –NO� , –CN, –CHO, –COR, -COOH, –COOR, –SO� H, etc.
 Q. Out of benzene, m–dinitrobenzene and toluene which will undergo nitration most easily and
why?

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Q. Arrange the following set of compounds in order of their decreasing relative reactivity with an
electrophile, E+

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(a) Chlorobenzene, 2,4-dinitrochlorobenzene, p-nitrochlorobenzene
(b) Toluene, p-CH� –C� H� -NO� , p-NO� –C� H�–NO�

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Q. How will you convert benzene into

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(i) p-nitrobromobenzene (ii) m- nitrochlorobenzene
(iii) p - nitrotoluene (iv) acetophenone?

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Hydrolysis
CaC2  Re d hot Cu tube
 A  B Cl2  FeCl3
  C here C is
(a) 𝐶� 𝐻� (b) 𝐶� 𝐻� 𝑁𝑂� (c) 𝐶� 𝐻� 𝐶𝑙 (d) 𝐶� 𝐻� − 𝑆𝑂� 𝐻
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Q. Identify the correct order of reactivity in electrophilic substitution reactions of the following
compounds-
CH3 Cl NO2
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1 2 3 4
(A) 1> 2 > 3 > 4 (B) 4 > 3 > 2 > 1 (C) 2 > 1 > 3 > 4 (D) 2 > 3 > 1 > 4
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Carcinogenicity and toxicity:

Benzene and polynuclear hydrocarbons containing more than two benzene rings fused together are
toxic and said to possess cancer producing (carcinogenic) property.
Such polynuclear hydrocarbons are formed on incomplete combustion of organic materials like
tobacco, coal and petroleum.
They enter into human body and undergo various biochemical reactions and finally damage DNA
and cause cancer.

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