UNIT – XIII Hydrocarbons 12hrs

SyllabusClassification of hydrocarbons. Alkanes: nomenclature (upto 5 carbon atoms), isomerism,physical properties. Preparation by:
hydrogenation of alkene and alkyne, examples (ethene, propene), from alkylhalide (reduction) and Wurtz reactions( methy and ethyl
halides), Kolbe’s electrolytic method for CH 3COONa (details of process not required). Chemical properties: substitution reaction -
halogenation - chlorination - mechanism, combustion (CH 4, C4H10), controlled oxidation (CH4 to CH3OH, H CHO), aromatization (for
hexane) pyrolysis. Conformational isomerism: conformations- sawhorse and Newman projection formulae for eclipsed and staggered
forms of ethane - compare stability and dihedral angle. Alkenes: nomenclature (upto 5 carbon), structure of double bond (ethene, bond
types and number).Geometrical isomerism – explain it as a type of stereoisomerism, cis and trans isomers,example – 2-butene. Physical
properties.
Preparation: by hydrogenation of 2-butyne– by Lindlar’s catalyst to get cis and Na/NH 3 to get trans isomers of 2-
butene,dehydrohalogenation of alkyl halide, dehalogenation of vicinal halides- examples taking ethyl bromide and 2-cholopropane,1,2-
dibromoethane, dehydration – ethene from alcohol. Properties – chemical properties – addition reactions of ethene with H 2, Cl2, Br2 /
CCl4 (test for unsaturation). Markovnikoff’s rule, addition of HBr to propene, mechanism, peroxide effect – for propene with HBr,
addition of water to ethene and propene, oxidation (Baeyer’s reagent) of ethene, ozonolysis (identification of products for ethene, propene,
2-butene), polymerization, uses. Alkynes: nomenclature (up to 5 carbon), isomerism, structure of triple bond (ethyne-types of bonds and
number). Preparation of ethyne – from calcium carbide, 1, 2-dibromoethane. Chemical properties for ethyne: acidic character – reaction
with sodium metal, addition reactions with –H 2, Br2, HBr, H2O. Polymerization – example for linear polymer, ethyne to benzene.
Aromatic hydrocarbons: Introduction, IUPAC nomenclature, isomerism (position–o, p, m), structure of benzene – kekule structures,
resonance and stability of benzene, aromaticity – characteristics for aromaticity (Huckel rule) – examples - benzene, cyclopentadienyl
anion, naphthalene. Chemical properties of benzene – electrophilic substitution reactions- halogenation, nitration, sulphonation, Friedel-
carfts alkylation (R X where R = -CH3, -C2H5), acylation (CH3COCl, (CH3CO)2O), benzene into hexachlorobenzene, addition reaction
with H2, Cl2. Mechanism of electrophilic substitution reaction – chlorination, nitration, alkylation (with CH 3Cl) acylation (CH3COCl).
Directive influence of a functional group in benzene – ortho and para directing groups (- OH, -OCH3,
-Cl, -CH3) and meta directing groups ( -NO2, -CHO, -COOH) with examples. Carcinogenicity and toxicity of benzene and polynuclear
hydrocarbons to be mentioned.

Hydrocarbons are the group of organic compounds containing only carbon and hydrogens.

Classification of hydrocarbons:- Hydrocarbons are mainly classified into 3 types

1) Saturated hydrocarbons
2) Unsaturated hydrocarbons
3) Aromatic hydrocarbons

1) Saturated hydrocarbons :- Saturated hydrocarbons are hydrocarbon in which carbon atoms are joined
only through the single bonds. saturated hydrocarbons are of two types
They are i) Alkanes and Cycloalkanes
Alkanes: Alkanes are saturated hydrocarbons in which carbon atoms are joined through the single bonds
to form a open chain. They are represented by general formula CnH2n+2
Ex: Methane (CH4), Ethane (C2H6) , Propane (C3H8) etc
Cycloalkanes:- Cycloalkanes are saturated hydrocarbons in which carbon atoms are joined through the
single bond to form a ring. They are represented by the general formula CnH2n
Ex: Cyclopropane ( ), Cyclobutane ( ), Cyclopentane ( )

2) Unsaturated hydrocarbons: Unsaturated hydrocarbons are hydrocarbons containing atleast one

( - C = C - ) or ( - C  C - ) in their molecules.
Ex: Ethene (C2H4) , propene (C3H6) , cyclobutene (C4H6) , Ethyne (C2H2) , propyne (C3H4)
3) Aromatic hydrocarbons:- Aromatic hydrocarbons are hydrocarbons containing atleast one benzene
ring in their molecules.
Ex: Benzene (C6H6) , Toluene (C7H8) , Naphthalene (C10H8) etc.

Alkanes: CnH2n+2 = The common and IUPAC names of some important alkanes are as follows.
 Formula Common name IUPAC name
1) CH4 Methane Methane
2) C2H6 Ethane Ethane
3) CH3-CH2-CH3 Propane Propane
4) CH3-CH2-CH2-CH3 n-butane Butane
5) CH3
Iso butane 2-methyl propane
CH3-CH-CH3

6) CH3-(CH2)3-CH3l n-pentane Pentane

7) CH3
Isopentane 2-methyl butane
CH3-CH-CH2-CH3

CH3 neo pentane 2,2 dimethyl propane

8) CH3-C-CH3
CH3

Isomerism in alkanes:-
First three members of alkanes donot exhibit isomerism but ligher members of alkanes exhibit chain
isomerism.
For ex: 1) Butane (C4H10) exists in 2 isomeric form
n – butane and isobutane
CH3-CH2-CH2-CH3 CH3

CH 3-CH-CH3

2) Pentane (C5H12) exists in 3 isomeric form

i) n – pentane ii) isopentane iii) neo-pentane
CH3-(CH2)3-CH3 CH3 CH3

CH 3-CH-CH2-CH3 CH3-CH-CH3

CH 3
3) Hexane (C6H14) exists in 5 isomeric forms. Their formula and IUPAC names are given below

i) CH3-CH2-CH2-CH2-CH2-CH3
Hexane ( N-Hexane)

CH3

ii) CH3-CH-CH2-CH2-CH3
2 methyl pentane , ( Iso hexane)

CH3

iii) CH3-CH2-CH-CH2-CH3
3 methyl pentane
 CH3 CH3

iv) CH3-CH-CH-CH3
2,3 dimethyl butane

CH3

v) CH3-C- CH2-CH3

CH3
2,2 dimethyl butane (neo hexane)
Methods of preparation of alkanes:
Method I:-
From Alkynes : Alkanes are prepared by the catalytic hydrogenation of alkenes in the presence of nickel
catalyst at 2000 C

R – CH = CH – R1 + H2 Ni
R – CH2 – CH2 – R1
0
200 C
Ex 1 : Ethane is prepared by heating ethene with dihydrogen (H2) in presence of nickel catalyst at 2000 C.
Ni
CH2 = CH2 + H2 CH3 – CH3
2000 C
Ex 2 : Propane is prepared by heating propene with dihydrogen (H2) in presence of nickel catalyst at 2000
C.
Ni
CH3 – CH = CH2 + H2 CH3– CH2 – CH3
2000 C

Method II:-

From Alkynes: Alkanes are prepared by heating alkynes with dihydrogen in presence of nickel catalyst
at 2000 C.

R – CH  C – R1 + 2H2 Ni
R – CH2 – CH2 – R1
0
200 C
Ex 1 : Ethane is prepared by heating ethyne with dihydrogen (H2) in presence of nickel catalyst at 2000 C.
HC  CH + 2H2 Ni
CH3 – CH3
2000 C
Ex 2 : Propane is prepared by heating propyne with dihydrogen (H2) in presence of nickel catalyst at 2000
C.
CH3 – C  CH + 2H2 Ni
CH3– CH2 – CH3
2000 C

Method III:-

From Alkyl halides (RX): Alkanes are prepared by the reduction of alkyl halides with zinc and dilute
HCl.
Zn/HCl
RX + 2 [H] RH + HX
Alkyl halide Alkane

Ex 1 : Methane is prepared by the reducing of methyl iodide ( Iodo methane) with zinc and dilute HCl.
Zn/HCl
CH3 I + 2 [H] CH4 + HI

Ex 2 : Ethane is prepared by the reducing of Bromo ethane with zinc and dilute HCl.
Zn/HCl
CH3 – CH2 – Br + 2 [H] CH3 – CH3 + HBr
Method IV:-
Preparation of higher alkanes from alkyl halides (Wurtz reaction)
Higher alkanes is prepared by heating an alkyl –halide with sodium metal in dry ether
dry ether
2 RX + 2 Na R–R + 2 Na X


Ex 1:- Ethane is prepared by heating iodo methane with sodium metal in dry ether.
dry ether
2 CH3 I + 2 Na CH3 – CH3 + 2 NaI


Ex 2:- Butane is prepared by heating Bromo ethane with sodium metal in dry ether.
dry ether
2 CH3 – CH2 – Br + 2 Na CH3– CH2– CH2 – CH3 + 2 NaBr

Method V:-

By the de carboxylation of carboxylic acids (Removal of carbon dioxide form carboxylic acid)

When a sodium salt of the carboxylic acid is heated with soda lime, Alkane with one carbon atom less
than the carboxylic acid is formed. This reaction decarboxylation of carboxylic acid.

CaO
RCOONa + NaOH R–H + Na2CO3


Ex 1:- Methane is prepared by heating sodium ethanoate with soda lime.

CH3 COONa + NaOH CaO

CH4  + Na2CO3


Method VI:-

Kolbe’s’ electrolytic method: [ From sodium or potassium salt of carboxylic acids]

Alkanes are prepared by the electrolysis of a strong solution of sodium or potassium salt of carboxylic
acid.

2 RCOONa + 2 H2O Electrolysis

R – R + 2CO2 + 2 NaOH + H2 

Ex 1:- Ethane is prepared by the electrolysis of strong solution of sodium ethanoate (Sodium acetate)
2 CH3COONa + 2 H2O Electrolysis
CH3 – CH3 + 2CO2 + 2 NaOH + H2

Ex 2:- Butane is prepared by the electrolysis of sodium proponoate solution.

2 CH3 CH2COONa + 2 H2O Electrolysis
CH3 CH2 CH2 CH3 + 2CO2 + 2 NaOH + H2

Physical properties:

1. The alkanes up to four carbon atoms are gases (C 1 – C4). Alkanes upto C17 are liquids and still higher
members are solids.

2. Alkanes are insoluble in water, but soluble in organic solvents such as benzene, ether etc.

3. The boiling points of n-alkanes increases with increase in molecular mass. For every addition of CH 2
group. Boiling point increases by 20 – 300C.

4. As the branching increases, boiling point decreases. For example, n-Pentane (b. p. 36 0C); Iso-
pentane (b. p. 280C); Neo-pentane (b. p. 9.50C).
Chemical properties:
Alkanes are inert to acids, bases, oxidizing and reducing agents. However, they undergo substitution
reactions. During substitution reaction, the hydrogen atom of the alkane is replaced by another atom or
group of atoms.
1. Hologenation: It involves the replacement of one or more hydrogen atoms of alkanes by halogen
atoms.
a) Chlorination: Chlorination is carried out by the treatment of alkane with chlorine in the presence of
diffused sunlight. For ex:, methane reacts with chlorine in the presence of diffusion sunlight to give a
mixture of methyl chloride, methylene chloride, chloroform and carbon tetra chlorides.
sunlight (h)
(1) CH4 + Cl2 CH3Cl + HCl
Chloromethane
sunlight (h)
(2) CH3Cl + Cl2 CH2Cl2 + HCl
Dichloromethane
sunlight (h)
(3) CH2Cl2 + Cl2 CHCl3 + HCl
Trichloromethane
sunlight (h)
(4) CHCl3 + Cl2 CCl4 + HCl
Tetra chloromethane
It is found that reactivity of different halogens towards alkanes varies as F 2> Cl2> Br2> I2. The order of
reactivity of different types of hydrogens in alkanes is tertiary > secondary > primary.

Note: Iodine reacts with alkanes slowly in a reversible manner. Hence, it is carried out in the presence of
oxidizing agents such as iodic acid (HIO 3) or nitric acid (HNO3) which converts HI to I2 and prevents
backward reaction.
CH4 + I2 CH3I + HI

Mechanism of chlorination of methane: Chlorination of methane takes place by free radical mechanism,
It takes place in three steps.
Step 1. Chain Initiation:
Chlorine molecule absorbs energy from sunlight and undergoes homolytic fission to give two chlorine
free radicals
Cl – Cl h
2Cl
Step 2. Chain propagation:
(a) A chlorine free radical reacts with a methane forming a methyl free radical and HCl.
CH4 + Cl CH3 + HCl
(b) Methyl free radical attacks a chlorine molecule to form a methyl chloride and chlorine free radical
CH3 + Cl2 CH3Cl + Cl
These steps (a) & (b) repeat several times and a chain reaction occurs.
Step :- (3) Chain termination:
The chain reaction steps when the free radicals combine to form the products.
CH3 + Cl CH3Cl (Methyl chloride)

CH3 + CH3 C2H6 ( Ethane)

2. Combustion: Alkanes burn in air or oxygen to give carbon dioxide and water liberating large amount
of heat.
Ex:
CH4 + 2O2 CO2+ 2H2O; H= -ve
Note: When alkanes undergo incomplete combustion, they form carbon monoxide and carbon black.

3. Controlled oxidation: Alkanes on heating with limited amounts of air or oxygen at high pressure and
in the presence of suitable catalysts give a number of oxidation products.
Ex:
0
(i) 2 CH4 + O2 Cu/250 C 2CH3OH
100 atm

Methane Methyl alcohol

MO 2 O 3 /2750 C

(ii) CH4 + O2 HCHO +H2O



Ethane Formaldehyde
(CH3COO)2Mn
(iii) 2CH4 - CH3 + 3O2 2CH3-COOH + 2H2O


Ethane Acetic acid

(iv) Normal alkanes resist oxidation. But, alkanes having tertiary hydrogen are oxidised to alcohols
by potassium permanganate.

CH3 CH 3
KMnO4
CH3 – C – H + (O) CH3– C – OH

CH3 CH3
4. Isomerisation: n-Alkanes when heated with anhydrous aluminium chloride and hydrogen chloride gas
are converted to their branched chain isomers.
Ex:
CH 3
An. AlC3 HCl
CH3– CH2– CH2– CH3 / CH3– CH – CH3
200C, 35atm
n-butane iso-butane

5. Aromatisation: n-Alkanes having more than six carbon atoms when heated to 6000C at 10-20
atmospheric pressure in the presence of oxide of vanadium or chromium supported over alumina give
aromatic hydrocarbons.
CH3
CH2 CH3
V O / Al O 2 5
+ 4H2
2 3

CH2 CH 0
2600 C/10-20atm
CH2
Note: n-heptane on aromatization gives toluene.
6. Reaction with steam: Methane reacts with steam at 10000C in the presence of nickel catalyst to give
carbon monoxide and hydrogen.

CH4 + H2O Ni/1000 0 C CO + 3H2



It is used in the production of hydrogen gas.

7. Pyrolysis: The process of decomposition of organic compounds on heating is called pyrolysis (Greek:
Pyro=fire, Lysis=loosening). The process of thermal decomposition of alkanes into smaller molecules is
called cracking.
Pyrolysis generally requires a temperature in the range of 500 0C-8000C. If cracking is carried out in the
presence of catalyst like Silica, Alumina etc at a lower temperature, it is called catalytic cracking.
Ex:
C3H6 + C2H4 + CH4
Propene ethene methane
0
CH3 – (CH2)4 – CH3 500 / 600 C

C2H6 + C4H8
ethane butene
Conformations:
Two or more isomers which differ only in the spatial arrangement of atoms caused by the rotation
over a C–C single bond are called conformers. (OR) conformational isomers (OR) rotmers.
Chemists have adopted two ways of representing conformational isomers
1) Saw horse representations
2) Newman projection
Conformations of ethane:
Ethane molecule containing a C – C single bond with each carbon atom attached to three H atoms. The
rotation of C – C bond results into infinite numbers of spatial arrangements of hydrogen atoms attached to
one carbon atom with respect to hydrogen atoms attached to other carbon atom. These are called
conformational isomers or rotamers.
The two important conformers of ethane are eclipsed and staggered conformations. The most stable
conformation of ethane is staggered conformation and the least stable and the least stable conformation of
ethane is eclipsed conformation.
Saw horse projection of eclipsed and staggered confirmations of ethane are as follows.

The Newman projections of ethane are as follows:

Alkenes: Alkenes are unsaturated aliphatic hydrocarbon containing one carbon – carbon double bond.
They are also called olefins (Greek, Olefinat =oil forming) because lower members react with chlorine to
form oily products. They are represented by the general formula CnH2n.

Nomenclature: The common and IUPAC names of few important alkenes are as follows.

Structural formula Trivial name IUPAC name

CH2 = CH2 Ethylene Ethene
CH3 – CH = CH2 Propylene Propene
CH3 – CH2 – CH = CH2 -Butylene But-1-ene
CH3 – CH = CH – CH3 -Butylene But-2-ene
CH3
CH3 – C = CH2 Iso-butylene 2-Methylpropene

Isomerism:
Alkenes show both structural isomerism and stereoisomerism. The lowest member of alkenes
which shows structural isomerism is butene(C 4H8). The three possible structural isomers of butene are as
follows.
CH3
CH3 – CH2 – CH = CH2 CH3 – CH = CH – CH3 CH3 – C = CH2
(i) But-1-ene (ii) But-2-ene (iii) 2-Methylpropene
Structure I and II are position isomers while structures I and III & II and III are chain isomers.
Geometrical isomerism: Alkenes having same molecular formula and same structural formula but differ
in the spatial arrangement of atoms or group of atoms in the molecule due to the restricted rotation around
carbon to carbon double bond are called geometrical isomers. The geometrical isomers having similar
groups on the same side of the double bond are called cis-isomers whereas those having similar groups on
opposite side of the double bond are called trans-isomers. This isomerism is also called cis-trans
isomerism.

Conditions for geometrical isomerism:

1) There should be a double bond in the molecule.
2) The two atoms or groups attached to each double bonded carbon atoms should be different.
Cis-isomer is more polar than trans-isomer as in cis-isomer dipole moments do not cancel. Cis-isomers
have higher boiling points than trans-isomers due to higher polarity. Trans-isomers are more stable than
cis-isomers and trans-isomers are more closely packed than cis-isomers. Hence, trans-isomers have higher
melting points and densities.
The geometrical isomers of But-2-ene are given below:
CH3 CH3 CH3 H
C= C C= C
H H H CH 3
Cis- But-2-ene trans- But-2-ene
(  = 0.33D) (  = 0)

Methods of preparation:
1.From alkynes: (i) Alkynes when reduced with hydrogen in the presence of Lindlar’s catalyst(Palladium
supported over calcium carbonate which is deactivated with quinoline or sulphur) gives cis-alkene.
 R R1
R − C≡ C− R 1 + H 2⃗
Pd / CaCO 3 C= C
quinoline
H H
Cis- Alkene
ii) Alkynes when reduced with sodium in liquid ammonia forms trans alkenes.

R H
1
R − C≡ C− R +2 H⃗ Na/ liquid NH 3 C =C
H R1
Trans-alkene
For example:

CH 3 CH 3
⃗
Pd / CaCO 3 C =C
quinoline

H H
Cis- But-2-ene
CH3 – C  C – CH3

CH 3 H
⃗
Na/ liq NH 3 C =C
H CH 3
trans- But-2-ene
2. From alkyl halides: When alkyl halides are heated with alcoholic potash, dehydrohalgenation takes
place giving alkenes.
For example:
CH3 – CH2 – Br + KOH(alc) CH2 = CH2 + KBr + H2O
Ethyl bromide Ethene

Dehydro halogenations follows the order: tertiary alkyl halide>secondary>primary. The rate of the
reaction varies with different halogens as iodide > bromide > chloride. The formation of an alkene is
governed by Sayzeff’s rule.
Saytzeff’s rule: It states that “During the dehydro halogenation of alkyl halides, the ‘H’ atoms is
eliminated from the -carbonatom which carries lesser number of hydrogens.
CH2 = CH – CH2 – CH3
Bue-1-ene (Minor product)
CH3 – CH – CH2 – CH3 KOH ( alc )

Br CH3 – CH = CH– CH3
Bue-2-ene (Major product)
3. From vicinal di halides: Vicinal di hlaides react with Zinc to form alkene.
This reaction is known as dehalogenation.
Ex:
CH2– Br  CH2
+ Zn + ZnBr2
CH2– Br CH2
1,2-Dibromoethane Ethene

CH2– CH– CH2 

+ Zn CH3 – CH = CH2 + ZnBr2
Br Br
1,2-Dibromo propane Propene
4. From alcohols: When alcohols are heated with excess of concentrated sulphuric acid at 170 0C they
undergo dehydration to give alkenes.
R − CH 2 −CH 2 −OH⃗
Conc . H 2 SO4 R −CH =CH 2 + H 2 O
1700 C

Alcohol Alkene
CH 3 −CH 2 −OH⃗
Conc . H 2 SO 4 CH 2 =CH 2 + H 2 O
1700 C

Ethyl alcohol Ethene

Physical properties:
1) The first three members are gases, the next fourteen are liquids and still higher members are solids.
2) Alkenes are generally insoluble in water but soluble in organic solvents like CCl 4, Hexane etc.
3) The boiling points of alkenes increases with increase in molecular mass. Normal alkenes have higher
boiling points than the branched chain alkenes.
4) Cis-isomers have lower melting points than trans-isomers because trans-isomers fit into the crystal
structure better than the cis-isomers.
Chemical properties:
Alkenes are reactive due to the presence of  bond. As -electrons are easily available, they undergo
electrophilic addition reactions. Under special conditions, free radical addition can also take place.
1.Addition of hydrogen: Alkenes react with hydrogen in the presence of nickel, platinum orpalladium
catalyst to give alkanes. This process is known as catalytic hydrogenation.
R − CH =CH 2 + H 2⃗
Ni R − CH 2 −CH 3
Δ

Alkene Alkane
CH 2 =CH 2 + H 2 ⃗
Ni CH 3−CH 3
Ex: Δ

Alkene Alkane
2. Addition of halogens: Halogens (Cl2 or Br2) react with alkenes in the presence of inert solvents like
carbon tetrachlorides to form dihaloalkanes.
 R−CH =CH 2 + Br 2⃗
CCl 4 R−CH −CH 2

Br Br
Dihaloalkane
Example:

CH 2 =CH 2 +Br 2⃗
CCl4 CH 2 −CH 2
Br Br
Ethene 1,2-Dibromoethane

3. Addition of hydrogen halides: Alkenes reacts with hydrogen halides to form alkyl halides.

R−CH =CH 2 + HX ⃗ R−CH −CH 3

X
Alkyl halide
Note: 1) The order of reactivity among hydrogen halides is HI > HBr > HCl > HF.
2) The addition of HX is governed by Morkownikoff’s rule which was given by Russian chemist
Morkownikoff’s in 1869.

Morkownikoff’s rule: When an unsymmetrical reagent adds to the unsymmetrical alkene, then the
negative part of the reagent adds to the carbon involved in the double bond containing least number of
hydrogen atoms.
Examples:

CH 3 −CH =CH 2 + HBr ⃗ CH 3 −CH −CH 3

Br
Propene 2-Bromopropane

Mechanism of addition of hydrogen bromide to propene:

The reaction takes place in three steps.

Step 1: Hydrogen bromide dissociated to gives H+ and Br–
H – Br H+ + Br–
Step 2: The electrophile H+ attacks propene to form a carbocation.

CH3– CH2 – CH2

(a)
+
CH3 – CH = CH2 + H
CH 3 – CH – CH3
(b)
Of the two carbocations, secondary carbocation (b) is more stable than the primary carbocation (a).
Hence, only (b) is formed.
Step 3: The nucleophile Br– attacks carbocation (b) to from 2 –bromopropane.

CH 3 −CH −CH 3 +Br − ⃗ CH 3 −CH −CH 3

Br
2-Bromopropane
Anti-Markownikoff’s addition (Kharasch effect): Addition of hydrogen bromide to propene in the
presence of peroxide catalyst takes place against Markownikoff’s rule. It is also called peroxide effect or
Kharasch effect (Kharasch and Mayo, 1930).
 CH 3 −CH =CH 2 + HBr⃗
peroxide CH 3 −CH 2 −CH 2 − Br

n-Propyl bromide

4. Addition of sulphuric acid: Cold concentrated sulphuric acid is added to alkenes to form alkyl
hydrogen sulphates. The addition takes place in accordance with Morkownikoff’s rule.

R−CH =CH 2 + H 2 SO 4 ⃗ R−CH −CH 3

OSO 3 H

CH 3 −CH =CH 2 + H 2 SO 4 ⃗ CH 3−CH −CH 3

Ex: OSO 3 H
Propene Iso-propyl hydrogen sulphate

5. Addition of water: Water added to alkenes in the presence of acids to form alcohol.

CH 3 −CH =CH 2 + H 2 O ⃗
H + CH 3 −CH −CH 3

OH
Propene 2-Propanol

Oxidation: (a) Alkenes are oxidised bycold dilute alkalinepotassium permanganate solution (Baeyer’s
reagent) to produce Vicinal diols called glycols. Decolourisation of potassium permanganate is a test of
unsaturation.

CH 3 −CH =CH 2 + H 2 O+( O)⃗

KMnO4 /OH − CH 3 −CH −CH 2

OH OH
Propene Propane-1,2-diol
b) When alkenes are heated with acidified potassium permanganate or acidified potassium dichromate,
they are oxidised to ketones or carboxylic acids depending upon the nature of alkenes and experimental
condition.

CH 3 −CH =CH 2 +5( O )⃗

KMnO 4 / H + CH 3 COOH +CO 2 + H 2 O
Δ
Propene Acetic acid

CH 3 −CH =CH −CH 3 +4 ( O )⃗

KMnO 4 / H + 2 CH 3 COOH
Δ
But-2-ene Acetic acid
7. Ozonolysis: Ozone adds to alkenes to form an ozonide which is hydrolysed with zinc and water to give
aldehydes or ketones. This reaction is called ozonolysis.

O
⃗
H 2 O / Zn
CH3 – CH = CH2 + O3 CH3 – CH CH2 CH3CHO+ HCHO
Propene acetaldehyde Formaldehyde
O O

CH3
⃗
i ) O3
CH3 – C = CH2 ii ) H 2 O / Zn HCHO + (CH3)2CO
2-Methylpropene Acetone

POLYMERISATION:
The union of large number of simple molecules to form a huge molecule having very high
molecular mas is called polymerization.
The simple molecules used in the polymerization process are called monomers.
The huge molecule having higher molecular mass formed during polymerization reaction is called a
polymer.
Ex: 1) When ethene is heated under high temperature under pressure in presence of catalyst,
polymerization takes place to form polythene.

CH2=CH2 High temp/ pressure -(CH2-CH2)-n

ethene catalyst polythene

2. When propene is heated under high temperature under pressure in presence of catalyst. Polymerisation
takes place to form polypropene.

CH3-CH2=CH2 High temp/ pressure -(CH2-CH2)-n

propene catalyst CH3
Polypropylene
or
Polypropene

Alkynes
Alkynes are unsaturated aliphatic hydrocarbons containing a -CC- in their molecules.
Alkynes are represented by common general formula CnH2n-2.
Ex: Ethyne or Acetylene (C2H2)
Propyne (C3H4)
Butyne (C4H6) etc
The common and IUPAC names of some alkynes are given below.
Formula Common Name IUPAC
CHCH Acetylene Ethyne
CH3-CCH Methyl acetylene Propyne
CH3-CH2-CCH Ethyl acetylene but-1-yne
CH3-CC-CH3 Dimethyl acetylene but-2-yne
CH3-CH2-CH2-CCH n-propyl acetylene Pent-1-yne
CH3-CH2-CC-CH3 Ethyl methyl acetylene Pent-2-yne
CH3-CH-CCH Isopropyl acetylene 3-methyl but-1-yne

CH3
Isomerism in Alkynes:
Fist two members of the alkyne series donot exhibit isomerism. Butyne (C4H6) exhibit in two
isomeric forms they are
But-1-yne  CH3-CH2-CCH
But-2-yne  CH3-CC-CH3
These two are examples for position isomers
Pentyne (C5H8) exist in three isomeric forms.
Pent-1-yne  CH3-CH2-CH2-CCH ------- (1)
Pent-2-yne  CH3-CH2-CC-CH3 ------- (2)
3-methyl-but-1-yne  CH3-CH-CCH ------- (3)

CH3
In the above examples 1 and 2 are position isomers 1, 2 and 2, 3 are chain isomers.
Preparation of Alkynes:
1. Preparation of ethyne from calcium carbide:
Ethyne is prepared by treating calcium carbide with H2O (water)
CaC2+2H2O  Ca(OH)2 + C2H2
Ethyne
2. Preparation of Alkynes from vicinal dihalides:
Vicinal dihalides on heating with alcoholic potash dehydrohalogenation takes place to form
alkynile halide
H H
or haloalkene
H X which on
RCCR1
treatment with
+ alc KOH
X X
RC = CR1 sodamide gives
Alkenyl halide alkyne
Polypropylene
propene

Ex:
H X 1.
RC CR1 + Na X+ NH3
RC = CR1 + Na NH2 Alkenyl halide
Alkenyl halide
Polypropylene
Ethyne is prepared from 1, 2-dibromoethane as follows.
alc KOH, heat NaNH2
BrCH2CH2Br CH2=CHBr CHCH
-HBr -HBr
2. Propyne is prepared from 1, 2-dichloropropane as follows
Properties of Alkynes:
CH3CHCH2Cl Chemical
alc KOH NaNH2 properties:
CH3CH=CHCl CH3CCH
Cl -HCl -HCl Acidic
properties of
1,2- alkynes: In
Bromoethene Propyne alkynes, the
dichloropropane
hydrogen
atoms bonded to the sp hybridized carbon atoms are acidic in nature. They can be replaceable by strong
bases like metallic sodium or sodamide.
For example:
1. When ethyne is heated with sodium metal, monosodium ethynide and disodium ethynide are
formed with the liberation of dihydrogen gas
2CHCH + 2Na  2HCCNa + H2
Monosodium ethynide
1
CHCNa + Na  NaCCNa + 2 H2 
Disodium ethynide
2. When propyne is heated with sodium metal, sodium propynide is formed.
1
CH3CCH + Na  CH3CCNa + 2 H2
Sodium propynide

Addition reactions:
a) Addition of hydrongen:
When alkynes are heated with dihydrogen in presence of nickel catalyst at 200 0C alkanes are
formed.
R−C ≡C − R|+2 H 2 ⃗
Ni R −CH 2 −CH 2 − R
|

2000 C
Ex: 1) When ethyne is heated with dihydrogen in presence of nickel catalyst at 2000C ethane is formed.
HC≡CH +2 H 2 ⃗
Ni CH 3 −CH 3
2000 C
2) When propyne is heated with dihydrogen in presence of nickel catalyst at 2000C propane is formed.
CH 3 −C≡CH + 2 H 2 ⃗
Ni CH 3 −CH 2 −CH 3
2000 C

b) Addition of halogens:
Alkynes react with halogen in CCl4 is form tetrahaloalkanes.
X X
| |
| |
R−C≡C−R + 2 X 2 ⃗
CCl 4 R− C − C −R
| |
X X
Ex: 1) Acetylene or ethyne reacts with chlorine in CCl4 to form 1, 1, 2, 2, tetrachloroethane
Cl Cl
| |
HC≡CH + 2 Cl 2 ⃗
CCl 4 H− C − C −H
| |
Cl Cl
1, 1, 2, 2, tetrachloroethane (westron)
2) Propyne reacts with bromine in CCl4 to form 1, 1, 2, 2-tetra bromopropane.
Br Br
| |
CH 3 −C≡CH + 2 Br 2 ⃗
CCl 4 CH 3 − C − C −H
| |
Br Br
1, 1, 2, 2-tetra bromopropane

c) Addition of hydrogen halides [HX]:

Alkynes undergo addition reactions with hydrogen halides to form alkenyl halide which further
undergo addition reaction with hydrogen halides to form gemdihalides.

R−C≡C−H + HX ⃗ R−C =CH 2

|
X
Alkenyl halide (OH) haloalkene

X
|
C
R− | =CH 2 + HX ⃗ R−C −CH 3
X |
X
gemdihalide

Ex: 1) Ethyne reacts with HCl to form chloro ethane (vinyl chloride) which further reacts with HCl to
form 1, 1-dichloro ethane.
CH ≡CH + HCl ⃗ CH 2 =CHCl
l
Vinyl chloride

Br
|
CH 3 −C≡CH + HBr ⃗ CH 3 − C −CH 3
|
Br
2, 2 dibromo propane
d) Addition of water (H2O):
When an alkyne is heated with dil.H 2SO4 in presence of mercuric sulphate (HgSO 4) catalyst at 600C
0
or 330 K, addition of H2O takes place to form halidhydes or ketones.

dil H 2 SO4 R− C =CH 2 ⃗ R−C −CH 3

R−C≡CH + H 2 O ⃗ | ||
0
HgSO 4 60 C
OH O
Ex: 1) When ethyne is treated with dil H 2SO4 in presence of HgSO4 catalyst at 600C ethanol
(acetaldehyde) is formed.
O
dil H 2 SO 4 CH 2 =CH −OH ⃗ CH 3 − −H ¿ ¿
||
CH ≡CH +H 2 O ⃗
0
C
HgSO 4 60 C
¿ ¿
Ethanol acetaldehyde
2) When propyne is heated with dil. H2SO4 in presence of HgSO4 catalyst at 600C propanone
(acetone) is formed.

dil H 2 SO 4 CH 3 − C =CH 2 ⃗ CH 3 − C −CH 3

CH 3 −C≡CH + H 2 O ⃗ |
0 ||
HgSO 4 60 C
OH O
(acetone)

Polymerisation:
Linear polymerization: When ethyne is subjected for polymerization, under special conditions, linear
polymerization takes place to form polyacetylene or polyethyne. This polyacetylene is used as eelctrodes
in batteries.
2n CH≡CH⃗
Polymerisation−( CH=CH−CH=CH ) −n ¿ ¿
Polyacetylene

Cyclic polymerization:
W h e n e t h y n e i s
H
polymerization
takes place to form
H C benzene.
C H H
HC C C
Red hot iron tube
HCCH

OR
6000C
HC C C
CH H
C H

H
Ethyne Benzene
3 CH ≡CH⃗
red hot iron C 6 H 6
tube 6000 C
Aromatic hydrocarbons:
Aromatic hydrocarbons or arenes are compounds of carbon and hydrogen containing atleast one
benzene ring. Most of these compounds possess pleasant odour (Truck-Aromametal pleasant smell) and
therefore, these compounds were named as aromatic compounds.
Aromatic compounds containing benzene ring are known as benzenenoids and those not containing
a benzene ring are known as ‘non-benzenoids’. Some examples of arenes are
CH3 CH3 CH3-CH2 H3C-CH-CH3
CH3

 
Benzene Toluene 1,2 –dimethyl benzene Ethyl benzene Isopropyl benzene
(O-xylene) (Cumene)
Nomenclature and isomerism:
The homologues of benzene having alkyl group are named as alkyl benzenes in IUPAC system. A
few examples of derivatives of benzene are given below
CH3 CH3 CH3
CH3
CH3

 
 
 

CH3
1,2 –dimethyl benzene 1,3 –dimethyl benzene CH3
Methyl benzene
(o-xylene) (m-xylene) 1,4 –dimethyl benzene
(p-xylene)
Structure of benzene:
1. From elemental analysis and molecular mass determination, the molecular formula of benzene was
found to be C6H6.
2. Benzene adds three molecules of hydrogen in the presence of nickel catalyst to form cyclohexane
and benzene combines with ozone to form benzene triozonide.
These indicate the presence of three double bonds in benzene.
3. Benzene does not decolorize bromine in CCl4 and it doesnot decolourise cold alkaline KM nO4
solution. These tests indicate that the double bonds of benzene are not identical to these of alkenes.
4. Benzene reacts with bromide in presence of ferric bromide to form bromobenzene.
C6 H 6 +Br 2 ⃗
FeBr 3 C 6 H 5 Br +HBr
The formation of only one monobromo product indicates that all the six hydrogen atoms of
benzene are identical.
5. To account for the above facts, August Kekule in 1865 proposed a hexagonal structure with
alternate single and double bonds
H

H C H
C C

C C
H
H C

H
Benzene

6. If Kekule structure is correct structure for benzene, it should give two isomeric ortho
dibromobenzenes (a) and (b). But benzene gives only one ortho dibromobenzene.
 Br Br
Br Br

a b
7. To over-come this draw back, Kekule suggested that the double bonds are in rapid oscillation and
hence the two structures are in dynamic equilibrium with each other. The two structures are shown
below.

I II
8. Kekule structure fail to explain the following
a) Kekule structure fail explain the stability of benzene.
b) X-ray diffraction studies shown that the bond lengths of benzene are identical for C-C bonds
(139 pm) which in intermediate between carbon-carbon single bond (154 pm) and carbon-
carbon double bond (134 pm).

Valence bond theory (or)Resonance theory:

According to thistheory, the actual structure of benzene is a resonance hybrid of two Kekule’s structures.
These individual structures are called canonical structures or contributing structures. The actual structure
of benzene is neither structure I nor II. It is the hybrid of these two structures.Because of resonance, the pi
electrons of benzene are delocalized which gives extra stability to benzene.

Structure I structure II Resonance hybrid

Orbital theory of Benzene:

All the carbon atoms of benzene are SP2 hybridized. The three SP2 hybrid orbitals of carbon are
present in a plane with the angle of separation of 1200. Each carbon utilizes its three SP2 hybrid orbitals to
form three sigma bonds, with one hydrogen and two adjacent carbon atoms. Thus, totally six C – C sigma
bonds and six C – H sigma bonds are formed.
After the formation of sigma bonds, each carbon atom is left with one unhybridised ‘2P’ orbital. The six
half filled unhybridised ‘P’ orbitals are parallel to each other and perpendicular to the plane of the ring.
The six ‘P’ orbitals are equidistant and hence overlap laterally on both the sides forming a
delocalized ‘’ electron cloud which lies above and below the plane of the ring.
 Upper ‘’ electron cloud

( OR ) Hexagonal carbon ring

Lower ‘’ electron cloud

The delocalization of ‘’ electron gives an extra stability to the benzene ring. This theory
clearly explains all the properties of benzene.
Aromaticity: The following are the conditions for a cyclic system to be aromatic.
1) It must be planar
2) They should be delocalized by pi electrons
3) It should contain (4n+2) ‘’ electrons, where n = 0, 1, 2, 3 . . . .
This is known as Huckel’s rule of Aromaticity.
Ex:

Cycloproenyl cation Benzene Cyclopentadienyl anion

(n = 0, 2π) (n = 1, 6π) (n = 1, 6π)

Cycloheptarienyl cation Naphthalene

(n = 1, 6π) (n = 2, 10π)

Preparation of Benzene:
1) When sodium benzoate is heated with sodalime, benzene is formed.
COONa

+ NaOH CaO + Na 2CO3

heat

Sodium benzoate Benzene

2) When phenol is distilled with zinc dust, benzene is formed.
OH

+ Zn heat + ZnO

Phenol Benzene

Properties of benzene: Due to presence of delocalised pi electron cloud in a benzene molecule, benzene
does not undergo addition reactions very easily. Benzene undergoes electrophillic substitution reaction to
form substituted benzenes.

(I) Electrophillic substitution reactions.

The electrophillic substitution reactions are important and characteristic reactions of all
Aromatic compounds. The important electrophillic substitution reactions of benzene are as
follows

(a) Halogenation: [ The replacement of H by halogen]

Benzene reacts with chlorine in dark in pressure of halogen carriers like Iron or ferric
chloride (FeCl3) to give chlorobenzene.
H Cl
FeCl 3
+ Cl – Cl + HCl

Chlorobenzene

(b) Nitration: [ replacement of H by – NO2 group]

When benzene is heated with a nitrating mixture to 500C, Nitrobenzene is formed.

H NO 2
Conc. H 2SO4
+ HONO2 500 C + H2 O

Nitrobenzene
[Note: Nitrating mixture: Nitrating mixture is a equimolar mixture of concentrated nitric acid (HNO 3) &
concentrated H2SO4 ]

Sulphonation: [ replacement of H by SO3H]

When benzene is heated with a concentrated sulphuric acid at 80 0C, benzenesulphonicacid is
formed.

H SO 3H

+ HO-SO3 800 C + H2O

Benzenesulphonicacid
 (d) Friedel craft’s alkylation [replacement of H by alkyl group]
When benzene is heated with methyl chloride in presence of anhydrous aluminium chloride
catalyst, toluene [methylbenzene]is formed.

H CH 3
anydrousAlCl 3
+ Cl -CH3 800 C + HCl

Toluene

(e) Friedel craft’s acylation [replacement of H by acyl(R-CO) group]

When benzene is treated with acetyl chloride in presence of anhydrous aluminium chloride
catalyst, acetophenone is formed.

H CO-CH 3
anydrousAlCl 3
+ Cl – CO-CH3 800 C + HCl

Acetophenone
(II) Addition reactions of benzene:
a) With hydrogen
When benzene is heated with hydrogen in presence of nickel catalyst at 180 0C to 2000C ,
cyclohexane is formed.

Ni
+ 3 H2 1800 C
Cyclohexane

b) With chlorine
When benzene is treated with chlorine in presence of sunlight and in the absence of halogen
carriers, addition reaction takesplace to form benzenehexachloride (BHC) is formed.
sunlight
C6H6 + 3 Cl2 C6H6Cl6

benzenehexachloride
(III) Combustion:
Benzene burns in air with a sooty flame producing carbondioxide and water.

C 6 H6 + 15
/2O2 6CO2 +3H2O H = - q J

Mechanism of electrophilic substitution reactions of benzene.

I. Mechanism of halogenation of benzene

Step 1. Generation of an electrophile, Cl+(Chloronium ion)

Cl2 + FeCl3 Cl+ + FeCl4

Step 2. Attack of an electrophile, Cl +to benzene
The electrophile, Cl + attacks to the benzene ring and cyclic carbocation is formed.

Cl

+ Cl+ + H
The carbocation formed is resonance stabilized.
Step 3.The loss of proton:
The carbocation combines with FeCl4to give the products and the catalyst FeCl3 is regenerated.

Cl Cl
H
+ + FeCl4 + HCl + FeCl 3

Chlorobenzene
II. Mechanism of Nitration of Benzene.

Mechanism:
Step 1. Generation of an electrophile NO2+
HNO3 + H2SO4 NO2+ + H2O + HSO4

Step 2. The electrophile NO2+attacks to the benzene ring to form cyclic carbocation.

NO 2
+ NO2+ + H
Carbonation The carbonation formed is resonance stabilized.


Step 3 : The carbocation loses a proton to HSO4- to form nitrobenzene

NO2 NO2
H
+ + HSO4 + H2SO4

III.Mechanism of the Sulphonation of benzene:-

Step 1. Generation of an electrophile, SO3.

2H2SO4 SO3 + H3O+ + HSO4

Step 2. The electrophile attacks to the benzene ring to form carbocation.

SO 3
+
+ + SO3 H

The carbocation formed is resonance stabilized.

Step 3. The carbocation loses a proton to H2SO4 to form a benzene sulphonate ion.

SO 3 SO3
 + H + HSO4 + H2SO4

Step 4. Benzene sulphonate ion takes up a proton form H3O+ to form benzene sulphonic acid.

SO3 SO3H
+ H 3O+ + H 2O
IV. Mechanism of the Fridel craft’s alkylation:-
Step 1. Generation of an electrophile CH3+
CH3Cl + AlCl3 CH3+ + AlCl4

Step 2. The electrophile CH3+attacks to the benzene ring to form cyclic carbocation.
CH 3

+ CH3+ H

The carbocation formed is resonance stabilized.

Step 3. The carbocation loses a proton to AlCl4 to form toluene and catalyst is regenerated.

CH3 CH3

H + AlCl4 + HCl + AlCl 3

V. Mechanism of the Fridelcraft’s acylation:-

Step 1. Generation of an electrophile,CH3CO+
CH3COCl + AlCl3 CH3CO+ + AlCl4

Step 2. The electrophile CH3CO+ attacks to the benzene ring to form cyclic carbocation.
COCH 3

+ CH3CO + H

The carbocation formed is resonance stabilized.

Step 3. The cyclic carbocation loses a proton to AlCl 4to form acetophenone and catalyst is regenerated.

COCH3 COCH3

H + AlCl4 + HCl + AlCl 3

Directive influence of functional group in monosubstituted benzene:

When a monosubstitued benzene is subjected to further substitution, the substituent already present
directs the incoming group to a particular position giving either ortho and para or meta products. This is
referred as directive influence of the group. There are two types of substituents (1) Ortho and para
directing groups and (2) Meta directing groups.
Ortho and para directing groups: The groups which direct the incoming groups to ortho and para
positions are called ortho and para directing groups.
Examples:
-OH, -OR,-NH2,-NHR,-NR2,-R,-X
 Let us discuss the directive influence of - OH group in phenol.
+ + +
O–H O–H O–H O–H O–H

Resonance structures of phenol

Because of resonance effect, electron density increases at ortho and para positions in the benzene
ring. Due to - I effect of the OH group, electron density of benzene ring decreases. However, +R effect is
stronger than – I effect which activates the benzene ring for electrophilic substitution. These groups are
called activating groups which result in ortho and para substitution products.
In the case of aryl halides, halogens are deactivating because – I effect is stronger than +R effect.
Hence, overall electron density of the benzene ring decreases. Hence, in aryl halides, though substitution
takes place in ortho and para positions, the ring is deactivated.
Meta directing groups: The groups which direct the incoming group to the meta position are called meta
directing groups.
Examples:
-NO2,-CN,-CHO,-CO-COOH,-COOR and –SO3H.

Let us discuss the directive influence of nitro group in nitrobenzene

O O O O O O O O O O
N N N N N

Resonance structures of nitrobenzene

Because of resonance effect, electron density decreases at ortho and para positions in the benzene
ring. Due to –I effect of the NO2 group also electron density of benzene ring decreases. Hence, these
groups are called deactivating groups. Therefore, the electrophilic substitution takes place to
comparatively electron rich meta position.

Carcinogencity and toxicity:

 Benzene and polynuclear hydrocarbons are toxic and carcinogenic (cancer producing). These
hydrocarbons are produced by the incomplete combustion of organic substances like tobacco, coal and
petroleum. They enter into human body and undergo various biochemical reactions damaging DNA and
thus cause cancer. Some of the carcinogenic hydrocarbons are given below.

1,2 - benzanthracene

CH3

CH3 1,2 - benzpyrene

9,10- Dimethyl-1,2-benzanthracene

*******
Important questions
1) Which metal is used in wurtz reaction?
Sodium
2) What is Lindlar’s catalyst?
Pd supported over barium sulphate or calcium carbonate poisoned with quinoline or
sulphur
3) Give the tests to show that the given compound is an unsaturatedcompound
a) Bayer‟stest
b) Bromination
4) Why alkynes does not show geometricalisomerism?
As they are linear in structure.
 5) Which catalyst is used in Friedel’s craft reaction?
Anhydrous aluminium chloride.
6) Which hydrocarbon is main constituent ofCNG?
Methane.
7) What is cracking/pyrolysis?
The decomposition of higher alkane into a mixture of lower
alkanes,alkenes etc by the application of heat is calledpyrolysis/cracking.
8) How will you prepare benzene from sodiumbenzoate?

COONa

CaO
+ NaOH +Na2CO3
Benzene
9) State Markovnikov’srule.
It states that, negative part of the addendum(adding molecules) gets attached to that
carbon atom which possesses lesser number of hydrogen atoms.
10) Explain Wurtz reaction with an example. Where is itused?
Alkyl halides on treatment with sodium metal in dry ether solution gives higher alkanes.
This reaction is known as wurtz reaction.
CH3Br +2Na+BrCH3 CH3-CH3+ 2NaBr
Ethane
11) What do you understand by torsional angle? Which of the conformations
of ethane has the maximum & the minimum torsionalstrain?
The repulsive interaction between the electron clouds, which effects stability of a
conformation, is called torsional strain. Magnitude of torsional strain depends upon the
angle of rotation about C-C bond. This angle is called dihedral angle or torsional angle. Of
all the conformations of ethane, the staggered form has the least torsional strain &
eclipsed form has the maximum torsionalstrain.
12) What arehydrocarbons?
Organic compound containing carbon & hydrogen are called hydrocarbon.
13) What ishydrogenation?
The process of addition of dihydrogen gas to alkenes or alkynes in the presence of finely
divided catalyst like Pt, Pd or Ni to form alkanes is called hydrogenation.
14) What is decarboxylation? How do you prepare methane from sodium
acetate by decarboxylation? Write theequation.
The removal of CO2from molecules having –COOH group by using sodalime is called
decarboxylation. sodalime is a mixture of sodium hydroxide & calcium oxide.
Ex: Methane is formed when sodium acetate is heated strongly in the presence
ofsodalime.

CH3COONa+NaOH CH4+ Na2CO3

15) Describe the preparation of alkanes by Kolbe’s electrolyticmethod.
Alkanes are prepared by the electrolysis of concentrated aqueous solution of
sodium or potassium salt of saturated mono carboxylicacids.
2RCOONa+2H2O R-R + 2CO2+ NaOH +H2
16) Give the mechanism of chlorination of methane.
Mechanism of chlorination of methane: Chlorination of methane takes place by free radical
mechanism, It takes place in three steps.
Step 1. Chain Initiation:
Chlorine molecule absorbs energy from sunlight and undergoes homolytic fission to give two
chlorine free radicals
Cl – Cl h
2Cl
Step 2. Chain propagation:
(a) A chlorine free radical reacts with a methane forming a methyl free radical and HCl.
CH4 + Cl CH3 + HCl
(b) Methyl free radical attacks a chlorine molecule to form a methyl chloride and chlorine free
radical
CH3 + Cl2 CH3Cl + Cl
These steps (a) & (b) repeat several times and a chain reaction occurs.
Step :- (3) Chain termination:
The chain reaction steps when the free radicals combine to form the products.
CH3 + Cl CH3Cl (Methyl chloride)

CH3 + CH3 C2H6 ( Ethane)

Prakash C K, MDR P U College, Chikkamagaluru. 190

 17) How do you prepare acetylene from calcium carbide?

CaC2+2H2O C2H2+ Ca(OH)2

18) Give two limitations of Kekule structure.
1. Fails to explain unusual stability of benzene
2. Fails to explain preference to substitution reactions than addition reactions.
19) What type of hybridization take place in each carbon atom of benzene?
sp2
20) How many σ C-C, σ C-H, & π bonds are present in benzene?
3C-Cσ , 6C-Hσ & 3π bonds.
21) Name the electrophile produced during the nitration of benzene.
Nitronium ion (or) NO2+
22) What are meta directing groups. Giveexamples.
The substituents or groups which direct the incoming group to meta position called
meta directing groups.
-NO2, -CN,-CHO,-COOH , -SO3H

Prakash C K, MDR P U College, Chikkamagaluru. 191