88 ] Oswaal CBSE Chapterwise & Topicwise Revision Notes, CHEMISTRY, Class – XI

On making the amount of CO produced in equation (A) equal to the amount of CO used inequation (B) by
multiplying the equations (A) and (B) by 5 and 2 respectively; we find that each mole of oxygen liberated from
the compound will produce two moles of carbondioxide.
Thus, 88 g carbon dioxide is obtained if 32 g oxygen is liberated.
Let the mass of organic compound taken be m g
Mass of carbon dioxide produced be m1 g
32m1 gO 2
\ m1 g carbon dioxide is obtained from
88
32 × m1 × 100
\ Percentage of oxygen =
%
88× m

Know the Terms

Ø Adsorption Chromatography: It is a chromatographic technique which is based on the fact that different
compounds are adsorbed on an adsorbent at different degrees.
Ø Mixed melting point: The melting point of two thoroughly mixed substances is called mixed melting point. This
can also be used for ascertaining the purity of a compound.

Know the Facts

Ø Criteria of purity of organic compounds: The purity of an organic compound can be ascertained by determining
its some physical constants like m.p., b.p., specific gravity, refractive index and viscosity.
 

CHAPTER-13
HYDROCARBONS
TOPIC-1
Saturated Hydrocarbons (Alkanes)

Revision Notes
Ø Classification of Hydrocarbons : Hydrocarbons are the compounds of carbon and hydrogen only. Hydrocarbons
are mainly obtained from coal and petroleum, which are the major sources of energy. Hydrocarbons are classified
as saturated hydrocarbon, unsaturated hydrocarbon and aromatic hydrocarbon.
A hydrocarbon is said to be saturated if it contains only C—C single bonds. For example : Ethane CH3 —CH3.
Unsaturated hydrocarbons contain carbon-carbon multiple bonds i.e., double bonds, triple bonds or both. For
example : Ethene CH2=CH2.

Aromatic hydrocarbon compounds consists of at least one aromatic ring. For example : Benzene

Ø Alkanes : Alkanes are the simplest organic compounds made of carbon and hydrogen only. They have the general
formula CnH2n+2 (where n = 1, 2, 3 etc.) Alkanes contain strong C —C and C —H bonds. Therefore, this class of
hydrocarbons is relatively chemically inert. Hence, they are sometimes referred to as paraffins (Latin : parum
affinis = little affinity).
Ø Methane (CH4) is the first member of this family. In methane, carbon forms single bonds with four hydrogen
atoms. All H—C—H bond angles are of 109.5°. Methane has a tetrahedral structure. C—C and C—H bonds are
formed by head-on overlapping of sp3 hybrid orbitals of carbon and 1s orbitals of hydrogen atoms.
Ø Alkanes exhibit chain isomerism, position isomerism and conformational isomerism.
Ø 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°).
Ø Groups or substituents derived from alkanes by removal of one hydrogen atom is known as alkyl groups. Their
general formula is CnH2n+1.
Oswaal CBSE Chapterwise & Topicwise Revision Notes, CHEMISTRY, Class – XI [ 89
Ø Steps to write correct structure from the given IUPAC name :
(i) Write the longest chain of carbon atoms corresponding to the parent alkane.
(ii) Give number to carbon atoms.
(iii) The substituents are attached to the correct carbon atoms after their numbering.
(iv) Satisfy the valency of each carbon atom by putting the correct number of hydrogen atoms.
Ø Preparation of Alkanes :
(i) Alkanes can be prepared by hydrogenation of unsaturated hydrocarbons in the presence of catalyst (Ni, Pd or
Pt).
CH2 = CH2 + H2 Ni / Pd / Pt
  CH3—CH3
Ethene Ethane
HC ≡ CH + 2H2 Ni / Pd / Pt
  H3C—CH3
Ethyne Ethane
(ii) By reduction of alkyl halides- Alkanes can be prepared by the reduction of alkyl halides (except fluorides)
with zinc and dilute hydrochloric acid.
Zn , H 
CH3—Cl + H2 
 CH4 + HCl
Chloromethane Methane
(iii) Wurtz Reaction— This reaction is used to increase the length of the carbon chain.
dry ether
CH3Br + 2Na + BrCH3  CH3—CH3 + 2NaBr
(iv) Decarboxylation : 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.
CaO
CH3COO–Na+ + NaOH 

 CH4 + Na2CO3

Sodium ethonate

(v) Kolbe’s Electrolytic Method—

Electrolysis
2CH3COO– Na+ + H2O  → CH3—CH3 + 2CO2 + H2 + 2NaOH
Sodium acetate Ethane
Ø Physical properties : Alkanes are almost non-polar molecule. They possess weak van der Waals forces. Due to
the weak forces, the first four members, C1 to C4 are gases, C5 to C17 are liquids and those containing 18 carbon
atoms or more are solids at 298 K. They are colourless and odourless. With the increase of branching, the boiling
points of alkanes decrease as on increasing the branching, the molecule attains the shapes of a sphere, decreasing
surface area, thereby decreasing van der Waals forces. Alkanes with even number of carbon atoms have higher
melting points as compared to next higher or lower alkanes with odd number of carbon atoms.
Ø Chemical Properties :
(i) Substitution Reactions: One or more atom of alkanes is replaced by halogens, nitro group and sulphonic
acid group, e.g., halogenation.
hv
CH4 + Cl2  CH3Cl + HCl
Chloromethane
hv
CH3Cl + Cl2  CH2Cl2 + HCl
Dichloromethane
hv
CH2Cl2 + Cl2  CHCl3 + HCl
Trichloromethane
hv
CHCl3 + Cl2  CCl4 + HCl
Tetrachloromethane
Mechanism :

(i) Initiation : Homolysis of chlorine molecule in the presence of light or heat.
hv
Cl2 2Cl
(ii) Propagation : Chlorine free radical attacks the methane molecule and takes the reaction in the forward
direction by breraking the C–H bond to generate methyl free radical with the formation of H–Cl.
Cl + CH4 HCl + CH3
The methyl radical obtained attacks the second molecule of chlorine to form CH3–Cl with the liberation of
another chlorine free radical by homolysis of chlorine molecule.
CH3 + Cl2 CH3Cl + Cl
90 ] Oswaal CBSE Chapterwise & Topicwise Revision Notes, CHEMISTRY, Class – XI

(iii) Termination :
C + Cl Cl2
CH 3 + CH 3 CH3—CH3
3 Cl + CH CH 3Cl
(ii) Combustion—Due to the evolution of a large amount of heat during combustion, alkanes are used as fuels.

 3n+1 
CnH2n + 2 +   O2 → nCO2 + (n + 1)H2O
 2 
13
e.g., C4H10 (g) + O (g) → 4CO2(g) + 5H2O (l); ΔH° = – 2875.84 kJ mol–1
2 2

(iii) Controlled Oxidation :

(i) 2CH4 + O2 Cu / 523 K / 100 atm
  2CH3OH
Methanol
Mo O
(ii) CH4 + O2 
2 3

 HCHO + H2O
Methanal
3  CH COO  Mn
(iii) 2CH3CH3 + 3O2 
2
 2CH3COOH + 2H2O
Ethanoic acid
KMnO
(iv) (CH3)3CH  O
4
 (CH3)3COH
2-Methylpropane 2-Methylpropan-2-ol
(3°-alkane)
(iv) Isomerisation— n-Alkanes on heating in the presence of anhydrous aluminium chloride and hydrogen
chloride gas isomerise to branched chain alkanes.
CH3 CH3CH2—CH—CH2—CH3
+
—

—
Anhyd. AlCl3/HCl
CH3(CH2)4CH3 CH2CH—(CH2)2—CH3 CH3
n-hexane 2-methylpentane 3-methylpentane
(v) Aromatization or Reforming—Dehydrogenation and cyclization to benzene and its homologues.
CH3

H2 C CH3
Cr2 O3 or V2O5

H2 C CH2 or Mo2O3, 773 K,

10-20 atm
Benzene
CH2
n–Hexane

(vi) Reaction with steam—(Industrial preparation of dihydrogen gas)

Ni ( 1273 K )
CH4 + H2O 
∆
→ CO + 3H2

(vii) Pyrolysis—Decomposition of higher alkanes to lower alkanes by the application of heat is called pyrolysis or
cracking.
C6H12 + H2
773 K
C6H14 C 4 H 8 + C2 H6

C3H6 + C2H4 + CH4

Ø Conformations of Alkanes : Alkanes have C—C sigma (s) bonds and rotation about C—C single bond is allowed.
This rotation results in different spatial arrangements of atoms in space which can change into one another, such
spatial arrangements are called conformations or conformers or rotamers. Alkanes can have infinite number
of conformations. Ethane shows eclipsed, staggered and skew conformations. Eclipsed form is least stable but
staggered form is most stable due to greater distance between the bond pairs or lesser torsional strain. The energy
difference between the two extreme forms is of the order of 12.5 kJ mol–1.
(i) Seahorse projections : In this projection, the molecule is viewed along the molecular axis.
Oswaal CBSE Chapterwise & Topicwise Revision Notes, CHEMISTRY, Class – XI [ 91
H
H H
H H H
H H

H H H H
(i) Eclipsed (ii) Staggered
(ii) Newman projections : In this projection, the molecule is viewed at the C–C bond head on.
Angle of rotation or
H H H
angle of tortion or
H H dihedral angle

H
H H H H
H
(i) Eclipsed H
(ii) Staggered

Know the Terms

Ø Cycloalkanes : Cyclic hydrocarbons having molecular formula CnH2n. These are isomeric with alkenes.
Ø Cracking : The process of breaking down less volatile higher molecular mass hydrocarbons from petroleum into
different types of more volatile lower molecular mass hydrocarbons by heating in the presence of catalyst.
Ø Reforming : Cyclization followed by aromatization (or dehydrogenation of 6-8 C alkanes on heating to 873 K in
the presence of Pt catalyst (e.g., n-heptane → methyl cyclohexane → toluene).
Ø Knocking : A sharp metallic rattling sound produced in an internal combustion engine.
Ø Octane Number : A scale for determining knocking quality in petrol. n-Heptane with very high knocking has
octane number 0 while iso-octane has maximum value 100.
Ø Cetane Number : A scale for determining knocking quality of a diesel fuel. Cetane number of n-hexadecane
(cetane) is 100 and that of a-methylnapthalene is zero.

Know the Facts

Ø Iodination is a reversible reaction. So it is carried out by heating alkane in the presence of oxidising agent like iodic
acid (HIO3) or nitric acid (HNO3) or mercuric oxide (HgO) which oxidises HI formed during the reaction.
CH4 + I2  CH3I + HI
HIO3 + 5HI → 3I2 + 3H2O
Ø Fluorination of alkane takes place explosively resulting even in the rupture of C—C bond in higher alkanes.
Ø Petroleum is an important source of aliphatic hydrocarbons. It is refined in to several useful fractions and is a
source of several petrochemicals. Coal tar is a rich source of aromatic hydrocarbons.
Ø LPG and CNG are petroleum products used as energy source in automobile industry and domestic fuel. Natural
gas contains about 90% CH4.

TOPIC-2
Unsaturated Hydrocarbons (Alkenes and Alkynes)

Revision Notes
Ø Alkenes : These are unsaturated non-cyclic hydrocarbons containing at least one double bond and have sp2
-hybridisation with 120° bond angle. Alkenes are also called olefins [oil forming] which indicates their high
reactive nature. Alkenes have general formula CnH2n, where n = 2,3,4 …Example- C2 H4 (ethene), C3H6 (propene),
etc.
Ø Structure of Double Bond : Carbon-carbon double bond in alkenes consists of one strong sigma (s) bond (bond
enthalpy about 397 kJ mol–1) due to head-on overlapping of sp2 hybridised orbitals and one weak pi (π) bond
(bond enthalpy about 284 kJ mol–1) obtained by lateral or sideways overlapping of the two 2p orbitals of the two
carbon atoms. The double bond is shorter in bond length (134 pm) than the C–C single bond (154 pm).
92 ] Oswaal CBSE Chapterwise & Topicwise Revision Notes, CHEMISTRY, Class – XI

Ø Nomenclature :
(i) The longest chain of carbon atoms containing the double bond is selected.
(ii) Numbering of the chain is done from the end which is nearer to the double bond.
(iii) The suffix ‘ene’ replaces ‘ane’ of alkanes.
Ø Isomerism : Alkenes show chain, position and geometrical isomerism. Chain isomers have different chains of
carbon atoms, e.g.,

CH2 CH CH3
CH2 = CH—CH2—CH3 and
CH3
But-1-ene
2-Methyprop-1-ene
Position isomers differ in the position of double bonds.
CH2 = CH—CH2—CH3 and CH3—CH = CH—CH3
But-1-ene But-2-ene
The stereoisomerism is exhibited by alkenes due to difference in the spatial arrangement of groups around double
bonded carbon atoms. The simplest alkene that can exhibit geometrical isomerism is but-2-ene. Cis form of alkene
is more polar than the trans form.

H3 C CH3 H3 C H
C C C C
H H H CH3
cis-But-2-ene trans-But-2-ene

The boiling point of cis-form is more than the trans-form due to high polarity of cis-form. However, melting point
of transform is more than that the cis-form.
Ø Preparation of Alkenes :
(i) From alkynes : Alkynes on partial reduction with calculated amount of dihydrogen in the presence of
palladised charcoal partially deactivated with poisons like sulphur compounds or quinoline give alkenes.
Partially deactivated palladised charcoal is known as Lindlar’s catalyst.
R R'

/ C  S or quinoline C C
RC ≡ CR′+ H2 Pd
 

Lindlar ' s catalyst 
H H
cis-Alkene
R H
Na/liquid NH3
RC CR' + H2 C C

R'
H
trans-Alkene
(ii) From alkyl halides : Alkyl halides (R-X) on heating with alcoholic potash (potassium hydroxide
dissolved in alcohol) eliminate one molecule of halogen acid to form alkenes. This reaction is known as
dehydrohalogenation i.e., removal of halogen acid. This is example of b-elimination reaction, since hydrogen
atom is eliminated from the b carbon atom.
H H H H
 
alc. KOH C C
H3 C C C H

H X H H
(X = Cl, Br, I)
The rate of the reaction :
for halogens is : iodine > bromine > chlorine
for alkyl group is : tertiary > secondary > primary
(iii) From vicinal dihalides : Dihalides in which two halogen atoms are attached to two adjacent carbon atoms
are known as vicinal dihalides. Vicinal dihalides on treatment with zinc metal lose a molecule of ZnX2 to form
an alkene. The reaction is known as dehalogenation.
Oswaal CBSE Chapterwise & Topicwise Revision Notes, CHEMISTRY, Class – XI [ 93
CH3CHBr—CH2Br + Zn → CH3CH = CH2 + ZnBr2
(iv) From Alcohols : Alcohols on heating with concentrated sulphuric acid form alkenes with the elimination of
one water molecule. This reaction is known as acidic dehydration of alcohols.

Ø Physical Properties : Alkene as a class resembles alkanes in physical properties, except in types of isomerism and
difference in polar nature. Ethene is a colourless gas with a faint sweet smell. All other alkenes are colourless and
odourless, insoluble in water but fairly soluble in nonpolar solvents like benzene, petroleum, ether. Alkenes show
a regular increase in boiling point with increase in size.
Ø Chemical Properties : Alkenes undergo electrophilic addition reaction because of loosely held π-electrons.
(i) Addition of dihydrogen :
H
H2C = CH2 Ni   H C—CH
2
/ Pt / Pd 3 3
Ethene Ethane
(ii) Addition of halogen : This reaction is used for the test of unsaturation.
CH2 CH2

CCl4
H2C = CH2 + Br Br Br Br
(Reddish orange) (Colourless)
(iii) Addition of hydrogen halides : The order of reactivity of the hydrogen halide is HI > HBr > HCl.
(a) CH2 = CH2 + HBr → CH3—CH2—Br
(symmetrical alkene)
(b) However, addition of hydrogen halide to an unsymmetrical alkene takes place according to
Markovnikov's rule. This rule states that, “the negative part of the addendum (adding molecule) gets
attached to that carbon atom which possesses lesser number of hydrogen atoms”. e.g.,

Mechanism :
Hydrogen bromide provides an electrophile, H+, which attacks the double bond to form carbocation as :
3 2 1
H3C—CH = CH2 + H – Br
H+

+ +
H3C—CH2—CH2 + Br– H3C—CH—CH3 + Br–
(a) less stable (b) more stable
primary carbocation secondary carbocation
(i) The secondary carbocation is more stable than the primary carbocation, therefore, the former predominates
because it is formed at a faster rate.
(ii) The secondary carbocation is attacked by Br– ion to form the product.
Br
Br–
—

+
as : H3C—CH—CH3 H3C—CH—CH3
2-Bromopropan
Peroxide effect or Kharash effect or Anti-Markovnikov addition : In the presence of peroxide, addition of

HBr to unsymmetrical alkene takes place contrary to Markovnikov rule. This reaction is known as peroxide
or Kharash effect or anti-Markovnikov addition. e.g.,
(C6H5CO)2O2
H3 C CH CH2 + HBr CH3 CH2 CH2Br
1-Bromopropane
94 ] Oswaal CBSE Chapterwise & Topicwise Revision Notes, CHEMISTRY, Class – XI

This reaction proceeds by free radical mechanism. Peroxide effect is observed only in case of HBr and not in
case of H—Cl and H—I.
O O O

—
—

—
—

—
—
Homolysis
(i)
C6H5 — C — O — O — C — C6H5 2C6H5 — C — O 2C6H5 + CO2
Benzoyl peroxide
Homolysis
(ii) C6H5 + H — Br
C6H5 + Br

CH3—CH = CH2 + Br
Homolysis

(iii) CH3—CH—CH2 CH3—CH—CH2—Br

—

Br (b) more stable

(a) less stable secondary free radical
primary free radical
Homolysis
(iv) CH3—CH—CH2Br + H — Br CH3—CH2—CH2Br + Br
(major product)
Homolysis
(v) CH3—CH—CH2 + H — Br CH3—CH—CH3 + Br
—

Br Br
(minor product)

(iv) Addition of sulphuric acid :

O

CH2 = CH2 + H O S O H CH3—CH2—OSO2—OH (C2H5HSO4)

Ethyl hydrogen sulphate
O

(v) Addition of water : In presence of few drops of concentrated sulphuric acid alkenes react with water to form
alcohols, in accordance with the Markovnikov rule.

+ CH3
H
CH3—C = CH2 + H2O C—CH3
CH3
CH3 OH
2-Methylpropene
2-Methylpropan-2-ol

(vi) Oxidation :
(a) Oxidation with cold dilute, aqueous solution of potassium permanganate (Baeyer’s reagent). This
reaction is used as a test for unsaturation as it decolourises KMnO4 solution.

(b) Oxidation with acidic potassium permanganate or acidic potassium dichromate to ketones and/or acids.

(CH3)2C = CH2 KMnO
 4 /H
 (CH3)2C = O + CO2 + H2O
2-Methylpropene Propan-2-one

CH3—CH = CH—CH3 KMnO
 4 /H
 2CH3COOH
But-2-ene Ethanoic acid
Oswaal CBSE Chapterwise & Topicwise Revision Notes, CHEMISTRY, Class – XI [ 95
(vii) Ozonolysis :

(viii) 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. The large molecules thus obtained are called
polymers. This reaction is known as polymerisation. The simple compounds from which polymers are called
monomers.
High Temp. (Pressure)
n(CH2CH = CH2) —(—CH2—CH2—)n—
Catalyst
Polythene
Ø Alkynes : Alkynes are unsaturated hydrocarbons that contain at least one carbon-carbon triple bond. General
formula of alkyne is CnH2n-2 e.g., C2H2 (ethyne), C2H4 (propyne). The first and the most important member of this
series of hydrocarbons is acetylene, C2H2 and hence they are also called the acetylene.
Ø Structure : In ethyne, the carbon atoms are sp hybridised. Carbon-carbon sigma (s) bond is obtained by the heat
on overlapping of the two sp hybridised orbitals of the two carbon atoms. The remaining sp hybridised orbital of
each carbon atom undergoes overlapping along the internuclear axis with 1s orbital of each of the two hydrogen
atoms forming two C–H sigma bonds. H–C–C bond angle is of 180°. Ethyne H—C ≡ C—H is a linear molecule.
Ø Preparation of alkynes :
(i) From calcium carbide : Ethyne is prepared by treating calcium carbide with water. Calcium carbide is
prepared as follows:

CaCO3   CaO + CO2
Limestone Quicklime
CaO + 3C → CaC2 + CO
Calcium carbide
CaC2 + 2H2O → Ca(OH)2 + C2H2
Acetylene
(ii) From vicinal dihalides : When vicinal dihalides react with alcoholic potassium hydroxide then they
undergo dehydrohalogenation. One molecule of hydrogen halide is eliminated to form alkenyl halide which
on treatment with sodamide gives alkyne.

Ø Physical Properties : Physical properties of alkynes follow the same trend of alkenes and alkanes. First three
members are gases, the next eight are liquids and higher ones are solids. All alkynes are colourless. Ethyene has
characteristic odour. Other members are odourless. They are weakly polar in nature. Alkynes are insoluble in
water but soluble in organic solvents like ethers, carbon tetrachloride and benzene. Melting point, boiling point
and density increase with increase in molar mass.
Ø Chemical Properties : Alkynes show electrophilic as well as nucleophilic addition reactions.
(i) Acidic character of alkyne :
HC ≡ CH + Na → HC ≡ C–Na+ + ½H2
Monosodium ethynide
HC ≡ C–Na+ + Na → Na+C– ≡ C–Na+ + ½H2
Disodium ethynide
CH3—C ≡ C—H + Na+NH2– → CH3C ≡ C–Na+ + NH3
Sodium propynide
96 ] Oswaal CBSE Chapterwise & Topicwise Revision Notes, CHEMISTRY, Class – XI

This reaction can be used for the distinction among alkynes, alkenes and alkanes and even for distinguishing
terminal alkynes from non-terminal alkynes as only terminal alkynes undergo this reaction.
(ii) Addition reactions :

Alkynes undergo electrophilic addition reaction and addition to unsymmetrical alkynes takes place according
to Markovnikov's rule. The addition product formed depends upon the stability of vinylic cation.
(a) Addition of dihydrogen :
H
CH3—C ≡ CH + H2 Ni / Pd / Pt
 [CH3—CH = CH2]   CH3—CH2—CH3
2

Propyne Propene Propane
(b) Addition of halogens :

T

This reaction is used as a test of unsaturation as reddish orange colour of solution of bromine in CCl4
is decolourised.
(c) Addition of hydrogen halides :

(d) Addition of water :

Ethyne

Propyne

(e) Polymerization :
(1) Linear polymerization : Under suitable conditions, 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—
Acetylene → Polyacetylene
(2) Cyclic polymerization : Ethyne on passing through red hot iron tube at 873K undergoes cyclic
polymerization.

  
Oswaal CBSE Chapterwise & Topicwise Revision Notes, CHEMISTRY, Class – XI [ 97

Know the Terms

 Cis-isomer: The geometrical isomer in which two identical atoms or groups lie on the same side of the double
bond is called cis-isomer.
 Trans-isomer: The geometrical isomer in which two identical atoms or groups lie on the opposite sides of the
double bond is called trans-isomer.
 Acidic Dehydration of Alcohols: The reaction in which a water molecule is eliminated from the alcohol molecule
in the presence of an acid is called acidic dehydration of alcohols.
 Polymerization: The process by which a long chain like molecule is obtained by the intermolecular combination
of small molecules (monomers) is called polymerization.
Know the Facts
Ø Peroxide effect is applicable only to HBr and not to HF, HCl and HI. Addition of HF, HCl and HI takes place
according to Markovnikov’s rule even in the presence of peroxide.
Ø The alkaline potassium permanganate solution is known as Baeyer’s reagent. It has bright pink colour. It oxidises
alkenes to glycols which is colourless. This reaction is used as a test for the presence of double bond in a molecule.
This is also known as Baeyer test.
Ø Bromine water test and Baeyer’s test are used to detect the presence of double bond while ozonolysis is used to
detect the position of double bond.

TOPIC-3
Aromatic Hydrocarbons: Benzene

Revision Notes
Ø These hydrocarbons are also known as ‘arenes’. Most of the aromatic hydrocarbons 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.
Ø Benzene molecule is a planar or flat molecule in which all the carbon atoms are sp2 hybridised. It has hexagonal
ring of six carbon atoms with three double bonds at alternate positions. It is resonance stabilised and the structure
may be represented as given below.

or

(A) (B) (C)

Ø Isomerism : When two hydrogen atoms in benzene are replaced by two similar or different monovalent atoms 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.
Ø Structure of Benzene : August Kekule in 1865 proposed benzene having cyclic arrangement of six carbon atoms
with alternate single and double bonds and one hydrogen atom attached to each carbon atom.
H
—

H— — C— H
—
C C—
—

Or Or
— —
C— C— —
H C H
—

H
2
Ø Aromaticity : It is a property of the sp hybridised planar rings in which the p orbitals allow cyclic delocalization
of π electrons. Aromatic compounds have specific electronic structure in accordance with Huckel rule. The rule
states that all planar cyclic conjugated polyenes containing (4n + 2)π electrons where n = 0, 1, 2, … are aromatic
in nature.
98 ] Oswaal CBSE Chapterwise & Topicwise Revision Notes, CHEMISTRY, Class – XI

Ø Preparation of benzene :
(i) Cyclic polymerisation of ethyne : Ethyne on passing through red hot iron tube at 873 K undergoes cyclic
polymerisation. Three molecules polymerise to form benzene.

(ii) Decarboxylation of Aromatic acids : Sodium salt of benzoic acid on heating with sodalime gives benzene.
COONa

CaO
+ NaOH + Na2CO3


(iii) Reduction of Phenol : Phenol is reduced to benzene by passing its vapours over heated zinc dust.
OH
—

∆
+ Zn + ZnO

Ø Physical Properties : Aromatic hydrocarbons are non-polar molecules and are usually colourless liquids or solids
with a characteristic aroma. Benzene itself is a good solvent for many organic and inorganic substances e.g., fat,
resins, sulphur and iodine. It burns with a luminous, sooty flame in contrast to alkanes and alkenes which
usually burn with a bluish flame.
Ø Chemical Properties : Benzene undergoes following types of chemical reactions:
(a) Electrophilic Substitution Reaction
(b) Addition Reaction
Electrophilic Substitution Reactions : Aromatic hydrocarbons undergo electrophilic substitution reactions,

e.g., nitration, halogenation, sulphonation and Friedel-Craft alkylation/acylation.
(i) Nitration :
NO2
—

323-333 K
+ Conc. HNO3 + conc. H2SO4 + H 2O
(nitrating mixture)
Nitrobenzene
(ii) Halogenation :
Cl
—

Anhydrous AlCl3
+ Cl2 + HCl

Chlorobenzene
(iii) Sulphonation :
SO3H
—

SO3
+ H 2O
H2SO4(fuming)

Benzene Benzene sulphonic

acid
Oswaal CBSE Chapterwise & Topicwise Revision Notes, CHEMISTRY, Class – XI [ 99
(iv) Friedel-Crafts alkylation reaction:

(v) Friedel-Craft’s acylation reaction:
COCH3

Anhyd. AlCl3
+ CH3COCl + HCl

Acetyl chloride Acetophenone

Benzene on treatment with excess of chlorine in the presence of anhydrous AlCl3 can be chlorinated to
hexachlorobenzene (C6Cl6)
Cl
Cl Cl
Anhyd. AlCl3
+ 6Cl2 + 6HCl

Cl Cl
Cl
Hexachlorobenzene
(C6Cl6)
Addition reactions :
(a) Under vigorous conditions i.e. at high temperature and/or pressure in presence of nickel catalyst, hydrogenation
of benzene gives cyclohexane.
Ni
+ 3H2
High temp. & pressure

Cyclohexane
(b) Under UV light, three chlorine molecules add to benzene to produce benzene hexachloride, C6H6Cl6.
Cl
Cl Cl
UV
+ 3Cl2
500 K
Cl Cl
Cl
Benzene hexachloride
(BHC or gammaxane)
Combustion—When heated in air, benzene burns with sooty flame :
15
C6H6 + O2 → 6CO2 + 3H2O
2
Ø The presence of substituent groups in aromatic ring activates/deactivates electrophilic substitution and also
directs the orientation of incoming groups. Electron donating substituents facilitate further substitution with
incoming groups at o- and p-positions while electron attracting groups deactivate the ring with substitution at
m-position.
– CH3, – OH, – OR, – NH2, – NHR, – NR2 are electron donating (or activating groups) while – NO2, – CN, – CHO,
– COOH, – SO3H are electron withdrawing (or deactivating groups). Halogens (– Cl, – Br, – I) are o-, p-directing
but moderately deactivating (due to strong – I effect).
Ø Polynuclear aromatic hydrocarbons (PAHs) have a number of condensed benzene rings and are suspected
carcinogens (toxic and they are having cancer producing property). They are actually formed due to incomplete
combustion of some organic materials like tobacco, coal, petroleum etc.
For example : 1, 2-Benzanthracene, 1, 2-Benzpyrene etc.
100 ] Oswaal CBSE Chapterwise & Topicwise Revision Notes, CHEMISTRY, Class – XI

Know the Terms

Ø Arenes: Aromatic hydrocarbons are known as arenes.
Ø Aromaticity: It is a property of conjugated cycloalkenes in which the stabilization of the molecule is enhanced
due to the ability of the electrons in the p orbitals to delocalize. This acts as a framework to create a planar
molecule.

Know the Facts

Ø Originally fragrant substances were called aromatic compounds.
Ø In the laboratory, benzene was first prepared by heating benzoic acid or phthalic acid with calcium oxide.
Ø Most of the benzene is produced from petroleum.
Ø Compounds having atoms other than carbon in a ring system, which satisfies the conditions of aromaticity are
called heteroaromatics.

 

CHAPTER-14
ENVIRONMENTAL CHEMISTRY
TOPIC-1
Atmospheric Pollution

Revision Notes
Ø Environmental Chemistry : The branch of chemistry which deals with the study of the origin, transport,
reactions, effects and fates of chemical species in the environment is called Environmental chemistry. It includes
our surroundings as air, water, soil, forest etc.
Ø Environmental Pollution : Environmental pollution is the effect of undesirable changes in our surroundings that
have harmful effects on plants, animals and human beings.
Ø Pollutants : A substance which causes pollution is known as pollutant. Pollutants can be solid, liquid or gaseous
substances, present in higher concentration than in natural abundance. It can be produced due to human activities
or natural happenings.
Ø Atmospheric Pollution: The atmosphere that surrounds the earth is not of the same thickness at different heights.
Atmospheric pollution is generally studied as tropospheric and stratospheric pollution.
Ø Tropospheric Pollution: Tropospheric pollution occurs due to the presence of undesirable solid or gaseous
particles in the air.
Ø Two kinds of pollutants occur :
(i) Primary Pollutants : Pollutants which are emitted directly from the sources.
(ii) Secondary Pollutants : Pollutants which are formed in the atmosphere by chemical interaction among
primary pollutants.
Ø The following are the major gaseous and particulate pollutants present in the troposphere:
l Gaseous air pollutants: These are oxides of sulphur, nitrogen and carbon, hydrogen sulphide, hydrocarbons,
ozone and other oxidants.
l Particulate pollutants: These are dust, mist, fumes, smoke, smog etc.
(i) Gaseous air pollutants:
Oxides of Sulphur: Oxides of sulphur are produced when sulphur containing fossil fuel is burnt. The most
common species sulphur dioxide is a gas that is poisonous to both animals and plants.
2SO2(g) + O2(g) → 2SO3(g)

SO2(g) + O3(g) → SO3(g) + O2(g)

SO2(g) + H2O2(l) → H2SO4(aq)