15.

Hydrocarbons

Can you recall?

Hydrocarbons can be open chain or
1. What are hydrocarbons? cyclic. In accordance with presence or absence
2. Write structural formulae of the of carbon-carbon multiple bond (C=C and/ or
following compounds : propane, ethyne, C ≡ C) the hydrocarbons are called unsaturated
cyclobutane, ethene, benzene. or saturated. Cyclic unsaturated hydrocarbon
can be either aromatic or nonaromatic (Fig.
The compounds which contains carbon 15.1).
and hydrogen as the only elements are called
hydrocarbons.
Hydrocarbon

Open chain (aliphatic) Cyclic

Unsaturated
Saturated (alkane) (alkene, alkyne) Saturated (alicyclic) Unsaturated

Straight Branched Straight Branched Aromatic Nonaromatic

chain chain chain chain

Fig. 15.1 : Classification of hydrocarbon

Do you know ?
Internet my friend
Why are alkanes called paraffins?
Alkanes contain only carbon-carbon and Collect information about Hydrocarbon
carbon-hydrogen single covalent bonds.
They are chemically less reactive and do
Figure 15.2 shows IUPAC and common
not have much affinity for other chemicals.
names of stuctural isomers of C4H10 and C5H12.
Hence they are called paraffins.
The number of possible structural isomers
15.1 Alkanes increases rapidly with the increase in the
Alkanes are aliphatic saturated number of carbon atoms. (See the Table 15.1).
hydrocarbons containing carbon-carbon Table 15.1 : Alkanes and isomer number
and carbon-hydrogen single covalent bonds. Number of Alkane Number of isomers
You have learnt in Chapter 14 that alkanes Carbon
have general formula CnH2n+2 where 'n' stands 1 Methane No structural isomer
for the number of carbon atoms in the alkane 2 Ethane No structural isomer
molecule. 3 Propane No structural isomer
15.1.1 Isomerism in alkanes 4 Butane Two
Alkanes with more than three carbon
5 Pentane Three
atoms generally exhibit, structural isomerism
6 Hexane Five
and in particular, the chain isomerism (refer
to section 14.5.1)
233
 C4H10
H H H H Use your brain power
i.
H−C−C−C−C−H 1. Write the structures of all the chain
H H H H isomers of the saturated hydrocarbon
Butane (n-Butane) containing six carbon atoms.
ii. H 2. Write IUPAC names of all the above
H C H structures
H H
The resulting arrangements of
H C C C H
the atoms in space about the
H H H C - C single bond are called conformations.
2-Methylpropane (Isobutane) Innumerable conformations result on complete
C5H12 rotation of a C - C single bond through 360°.
In chapter 14 you have learnt about
isomerism. The phenomenon of existence of
H H H H H
i. conformation is a type of stereoisomerism. In
H−C−C−C−C−C−H conformational isomerism the conformations
(or conformational isomers) interconvert
H H H H H
Pentane (n-Pentane ) by rotation about a C - C single bond. Out of
infinite conformations of ethane molecule
ii. CH3 two are extreme and called staggered and
eclipsed conformation. They are represented
CH3 − CH − CH2 − CH3
by Sawhorse formula and Newman
2-Methylbutane (Isopentane )
projection formula as shown in Fig. 15.3.
iii. CH3 Conformational isomerism in other alkanes is
CH3 - C - CH3 more complex.
CH3 H
H H H
2,2-Dimethylpropane (Neopentane) H H
H H
Fig. 15.2 : Structural isomers of butane and H H H H
pentane
15.1.2 Conformations in alkanes : Alkanes Staggered Eclipsed
have only single bonded atoms. You have (a) Sawhorse formula
learnt that a single covalent bond is formed by H H HH
coaxial overlap of orbital and is called sigma H H H
(σ) bond (Refer to Chapter 5). As a direct H
H
consequence of coaxial overlap of orbitals, a HH
H
sigma bond is cylindrically symmetrical and Staggered Eclipsed
the extent of orbital overlap is unaffected by
(b) Newman Projection formula
rotation about the single bond and therefore
C-C bonds undergo rotation. The atoms Fig. 15.3 : Representation of staggered and
bonded to one carbon of a C-C single bond eclipsed conformation of ethanes
change their relative position with reference to
the atoms on the other carbon of that bond on
rotation of that C-C single bond.

234
15.1.3 Industrial preparation of alkanes
a. Industrial source : Crude petroleum and Try this
natural gas are the source of alkanes. Dead Transform the following word equation into
plants buried under earth billions of year ago balanced chemical equation and write at
got converted into crude oil under the high least 3 changes that occur at molecular level
temperature and pressure conditions. The crude during this chemical change.
oil collected in dome shaped cavities under the 2-Methylpropene+Hydrogen
catalyst
Isobutane
earth surface, which we call oil wells. Alkanes
are obtained by fractional distillation of crude 2. From alkyl halides
oil in oil refineries. a. By reduction of alkyl halides : Alkyl halides
b. Methods of preparation of alkanes : on reduction with zinc and dilute hydrochloric
acid form alkanes. The reduction of alkyl
Can you recall? halides is due to nascent hydrogen obtained
from the reducing agent Zn and dilute HCl.
• What is a catalyst ? Zn , HCl
• What is addition reaction ? CH3 - I + 2 [ H ] CH4 + HI
Methyl Nascent Methane
1. From unsaturated hydrocarbons : iodide
Catalytic hydrogenation of alkenes or alkynes Zn , HCl
CH3 - CH2 - Br + 2[ H ] 2 CH3 - CH3
with dihydrogen gas gives corresponding
alkane. Finely divided powder of platinum (Pt) Ethyl bromide Nascent Ethane
or palladium (Pd) catalyse the hydrogenation + HBr
of alkenes and alkynes at room temperature. b. By using reactive metal : In 19th century
Relatively high temperature and pressure alkyl halides were transformed to alkane
are required with finely divided nickel as the having double the number of carbons by Wurtz
catalyst. coupling reaction using the reactive metal
From alkenes sodium.
dry ether
H H H H CH3 - Br + 2Na + Br - CH3
Pt or Pd (room temp.)
H-C=C-H+H H H- C - C - H CH3 - CH3 + 2NaBr
or Ni H H
Ethene (high temp and
high pressure) Ethane Later bettter methods using metals such as
H H Mg, Li were developed. Grignard reaction is
H H Pt or Pd
(room temp.) one of the new methods widely employed for
H 3C - C = C - H + H H H3C- C - C - H
or Ni H H preparation of alkanes.
(high temp and
Propene high pressure) Propane Alkyl magnesium halides ( Grignard
From alkynes reagent) are obtained by treating alkyl halides
H H with dry metal magnesium in the presence of
H-C≡C-H+2H H Pt or Pd (room temp.) H- C - C - H dry ether. These on treatment with water give
or Ni H H alkanes.
(high temp and
Ethyene high pressure) Ethane dry ether
R − X + Mg R − Mg − X
Alkyl halide Alkyl magnesium halide
Pt or Pd (room temp.)
dry ether
CnH2n + H2 Or Ni (high temp.& high pressure) CnH2n+2 R−Mg−X + H−O−H R − H + MgX(OH)
Alkene Alkane Alkane
Pt or Pd (room temp.)
dry ether
CnH2n-2 + H2 Or Ni (high temp.& high pressure) CnH2n+2 CH3 - Mg - I + H - O - H CH3 - H + MgI(OH)
Alkyne Alkane Methyl Methane
magnesium iodide

235
 H H H H H
Do you know ? H−C−C−C−C−C−H
Prepartion of Grignard reagent is an H H H H H
exothermic reaction. Hence no heating is large surface area
H H H H H
required. In this reaction :
i. Magnesium metal gradually diappears. H−C−C−C−C−C−H
ii. Magnesium atoms gets bonded to the H H H H H
same carbon that previously held halogen.
iii. Alkyl group remains as it is or intact
CH3 CH3

small surface area

during the preparation grignard reagent.
H3C - C - CH3 H3C - C - CH3
iv. Dry and inert conditions are to be
maintained during Grignard reaction to CH3 CH3
prevent any reaction with moisture.

15.1.4 Physical properties of alkanes

i. Polarity : The electronegativity of carbon Fig. 15.4 : Relative surface area of straight
and hydrogen is nearly the same. C-H and chain and branched alkanes
C-C bonds are non-polar covalent bonds and
alkanes are, thus, nonpolar. The forces which Branched alkanes have lower melting
hold non-polar molecules together are the van and boiling points. Intermolecular forces are
der Waals forces. Those are usually weak. overcome partly during melting process and
Larger the surface area of molecules, stronger completely during boiling process. Table 15.2
are such intermolecular van der Waals forces. shows the melting and boiling points of some
The intermolecular forces are relatively alkanes. Alkanes are colourless and odourless.
stronger in straight chain alkanes than in At room temperature, the first four alkanes are
branched alkanes (See Fig. 15.4). gases, next alkanes having 5 to 17 carbons are
Therefore straight chain alkanes have higher liquids and carbons 18 onwards are solids.
melting and boiling points.

Use your brain power

Why are alkanes insoluble in water and readily soluble in organic solvents like
chloroform or ether ?
Table 15.2 : Melting and Boiling points in alkanes
Molecular formula Name Molecular mass/u b.p. (K) m.p. (K)
CH4 Methane 16 111.0 90.5
C2H6 Ethane 30 184.4 101.0
C3H8 Propane 44 230.9 85.3
C4H10 Butane 58 272.4 134.6
C4H10 2-Methylpropane 58 261.0 114.7
C5H12 Pentane 72 309.1 143.3
C5H12 2-Methylbutane 72 300.9 113.1
C5H12 2,2-Dimethylpropane 72 282.5 256.4
C6H14 Hexane 86 341.9 178.5

236
15.1.5 Chemical properties of alkanes : CH3 CH3
Cl2
Alkanes are relatively unreactive towards H3C - CH - CH3 H3C - CH - CH2 - Cl
UV light
acids, bases, oxidizing and reducing agents. 2-Methylpropane 1-Chloro-2-methylpropane
They undergo the following reactions under (36%)
specified conditions. CH3
1. Halogenation of alkanes : The reactions + H3C - C - CH3
in which an atom or group of atoms in a Cl
molecule is replaced by another atom or group 2-Chloro-2-methylpropane (64%)
of atoms are known as substitution reactions.
Bromination gives corresponding
Substitution of H atoms of alkanes by X
bromides, but in different proportions. For
(halogen, X= Cl, Br, I and F) atom is called
example,
halogenation of alkanes. Alkanes react with Br
halogens in presence of UV light or diffused H3C - CH3 UV light 2
H3C - CH2 - Br
sunlight or at higher temperature ( 573 To 773 Ethane Bromoethane
Br2
K) to give mixture of alkyl halides. H3C - CH2 - CH3 UVlight H3C - CH2 - CH2 - Br
Chlorination of methane : Propane 1-Bromopropane (3%)
H H + H3C - CH - CH3
UV light
H - C - H + Cl - Cl or ∆ H - C - Cl + H - Cl Br
2-Bromopropane (97%)
H H Br2
Methane Chlorine Chloromethane Hydrogen H3C-CH2-CH2-CH3 UV light H3C-CH2-CH2-CH2- Br
(Methyl chloride) chloride Butane 1-Bromobutane(2%)
H H
+ H3C - CH2 - CH - CH3
UV light
H - C - Cl + Cl -Cl or ∆
H - C - Cl + H - Cl Br
H Cl 2-Bromobutane (98%)
Chloromethane Dichloromethane CH3 CH3
Br2
H Cl H3C - CH - CH3 H3C - CH - CH3 - Br
UV light UV light
H - C - Cl + Cl - Cl or ∆ H - C - Cl + H - Cl 2-Methylpropane 1-Bromo-2-methylbutane
Cl Cl (trace)
Dichloromethane Trichloromethane CH3
Cl
UV light
Cl + H3C - C - CH3
H - C - Cl + Cl - Cl or ∆ Cl- C - Cl + H - Cl Br
Cl Cl 2-Bromo-2-methylpropane (over 99%)
Trichloromethane Tetrachloromethane
Tetrachloromethane is a major product In bromination, there is high degree of
when excess of chlorine is used. Chloromethane selectivity as to which hydrogen atoms are
is obtained as major product when excess replaced. Halogenation of alkanes follows the
of methane is employed. The reactivity of free radical mechanism. Homolysis of halogen
halogens toward alkanes follows the order molecule (X2) generates halogen atoms, that
F2 > Cl2 > Br2 > I2. is, halogen free radicals. The mechanism of
The ease of replacement of hydrogen atoms the first step of chlorination of methane is
from the carbon is in the order of shown below :
UV • •
30 > 20 > 10. Cl Cl homolysis Cl + Cl
For example, Cl (initiation)
2
H3C - CH2 - CH3 UV light H3C - CH2 - CH2 - Cl +
• •
Propane 1-Chloropropane ( 45%) H3C H + Cl H3C + H - Cl
H3C - CH - CH3
• •
Cl H3C + Cl Cl H3C - Cl + Cl
2-Chloropropane ( 55%) (propagation)
237
 in the presence of V2O5, Cr2O3 ,Mo2O3 etc.
Remember supported over alumina. The reaction involves
simultaneous dehydrogenation and cyclization.
1. Depending upon which hydrogen atom is
This reaction is known as aromatization or
replaced, a number of isomeric products
reforming .
can be formed from alkane. For example,
H3C - CH2 - CH2 - CH2 - CH2 - CH3
n-Butane and isobutane yield two isomers
n-Hexane
each.
V2O5
2. Halogenation an alkane yields a mixture 773K, 10-20 atm + 4H2
of all possible isomeric products,
indicating all the hydrogen atoms are Benzene
susceptible to substitution. This process is used in refineries to
produce high quality gasoline (the fuel used in
2. Combustion : Alkanes on heating in the automobiles).
presence of air or dioxygen are completely
oxidized to carbon dioxide and water with the
Use your brain power
evolution of a large amount of heat. That is
why alkanes are good fuels. Name the alkane from which methyl
CH4 + 2 O2 CO2 + 2 H2O ; benzene is obtained by reforming?
Methane
∆CH0 = - 890 kJ mol -1
Collect the information of CNG and LPG
C4H10 + 13/2 O2 4 CO2 + 5H2O ;
with reference to the constituents and the
Butane
advantages of CNG over LPG.
∆CH0 = - 2875.84 kJ mol -1
A representative combustion equation for 15.1.6 Uses of alkanes :
alkane is 1. First four alkanes are used as a fuel mainly
CnH2n+2 +

(
3 n+1
2
O2( n CO2
+ ( n + 1) H2O + Heat
for heating and cooking purpose. for example,
LPG and CNG.
2. CNG, petrol, diesel are used as fuels for
Can you recall? automobiles.
3. Lower liquid alkanes are used as solvent.
What is the product which is
4. Alkanes with more than 35 C atoms (tar) are
poisonous and causes air pollution formed
used for road surfacing.
by incomplete combustion of alkane ?
5. Waxes are high molecular weight alkanes.
3. Pyrolysis : Alkanes on heating at higher They are used as lubricants.They are also
temperature in absence of air decompose to used for the preparation of candles and carbon
lower alkanes, alkenes and hydrogen, etc. This black that is used in manufacture of printing
is known as pyrolysis or cracking. ink, shoe polish, etc.
C6H12 + H2
773 K
C6H14 C4H8 + C2H6
C3H6 + C2H4 + CH4 Can you recall?

4. Reforming : Straight chain alkanes • What are alkenes?

containing 6 to 10 carbon atoms are converted • Calculate the number of sigma (s ) and
to benzene and its homologues on heating pi (p) bonds in 2-Methylpropene ?
under 10 to 20 atm pressure at about 773 K • Write structural formula of pent-2-ene.

238
15.2 Alkenes : Alkenes are unsaturated Structure I and III along with II and III are
hydrocarbons containing at least one carbon- the examples of chain isomerism. They differ
carbon double bond. Alkenes with one carbon- in carbon chain length. Structure I and II are
carbon double bond, contain two hydrogen the examples of position isomerism because
atoms less than corresponding alkanes.They they differ in the position of double bond in the
have general formula CnH2n.where n= 2,3,4... same carbon chain.
etc. You have also learnt about the IUPAC ii. Geometrical isomerism
names of alkenes in Chapter 14. The isomerism which arises due to the
difference in spatial arrangement of atoms or
Do you know ? groups about doubly bonded carbon ( C=C)
atoms is called geometrical isomerism. If the
1. Alkenes are also known as olefins, two atoms or groups bonded to each end of the
because the first member ethylene or C=C double bond are different, then molecule
ethene reacts with chlorine to form oily can be represented by two different special
substance. arrangements of the groups as follows :
2. The aliphatic unsaturated hydrocarbon
containing two or three carbon-carbon X Y
X Y
double bonds are called alkadienes and C C

alkatrienes, respectively. for example,
C C
CH3 Y Y X
X
H2C = C − CH = CH2 Methylbuta-1,3-diene
(Isoprene) (A) (B)

In structure (A), two identical atoms

or groups lie on the same side of the double
bond. The geometrical isomer in which two
b-Phellandrene (oil of eucalyptus) identical or similar atoms or groups lie on
the same side of the double bond is called
15.2.1 Isomerism in alkenes : Alkenes with
cis-isomer.
more than three carbon atoms show both
In structure (B), two identical atoms or
structural isomerism and geometrical
groups lie on the opposite side of the double
isomerism.
bond. The geometrical isomer in which two
i. Structural isomerism : Alkenes with
identical or similar atoms or groups lie on
molecular formula C4H8 is butene. The
the opposite side of the double bond is called
structural formulae for C4H8 can be drawn in
trans-isomer. Due to different arrangement of
three diffferent ways :
1 2 3 4 atoms or groups in space, these isomers differ
H2C = CH − CH2 − CH3 in their physical properties like melting point,
(I) But-1-ene (Chain of 4 carbon atoms) boiling point, solubility etc. Geometrical or
cis-trans isomers of but-2-ene are represented
1 2 3 4 as :
H3C − CH = CH − CH3
(II) But-2-ene (Chain of 4 carbon atoms) H CH3 H CH3
C
C
CH3 C C
1 2 3 H CH3 H
H2C = C − CH3 H3C

(III) 2-Methylprop-1-ene (Chain of 3 carbon atoms) cis-But-2-ene trans- But-2-ene

(b.p. = 277 K) (b.p. = 274 K)

239
 The hydrogen atom from adjacent carbon
Do you know ? called b-carbon atom, is removed and the
reaction is known as b-elimination.
1. No terminal alkenes i.e. those with Dehydrohalogenation suffers from the
C=CH2 unit can exist as cis- and trans- disadvantage that -H can be eliminated from
isomers. the carbon on either side of the a-carbon
2. No 1,1-disubstituted alkenes i.e. those bearing the -X. When an alkyl halide is boiled
with C = CR2 unit can exist as cis- and with a hot concentrated alcoholic solution of
trans -isomers. a strong base like KOH or NaOH, alkene is
3. Alkenes with general formulae formed with removal of water molecule.
RCH=CHR, R1R2C = CR1R2, R1CH=CR1R2,
R1CH=CR2R3, R1CH=CHR2 and R1R2C= H H
CR3R4 exibit cis-trans isomerism. β α boil
H C C H + KOH
(alcoholic)
15.2 Preparation of alkenes H Br
a. Industrial sources : The most important Bromoethane
alkenes for chemical industry are ethene, H H
propene and buta-1,3-diene. Alkenes H C C H + KBr + H2O
containing upto four carbon atoms can be Ethene
obtained in pure form from the petroleum H H H H
products. Ethene is produced from natural gas β α β boil
H − C − C − C − C − H + KOH
and crude oil by cracking.
b. Methods of preparation of alkenes H Cl H H
(I) Elimination reactions : (1,2 -elimination ) 2-Chlorobutane alcoholic
H H H H H H H H
The reactions in which two atoms or groups are
eliminated or removed from adjacent carbon H-C=C-C-C-H + H-C-C=C-C-H
atoms are called 1,2 - elimination reactions. H H H H
But-1-ene (20%) But-2-ene (80%)
sp3 hybridized sp2 hybridized
+ KBr + H2O
−C−C− 1, 2-eliminaton
-XY
−C=C− In dehydrohalogenation of
Alkene
X Y 2-Chlorobutane, but-2-ene (disubstituted
alkene) is the preferred product because it is
Remember formed faster than but-1-ene ( monosubstituted
alkene). This is in accordance to with Saytzeff
1. The carbon - carbon double bond can
rule.
be generated from a carbon -carbon single
Saytzeff rule : In dehydrohalogenation the
bond by elimination reaction.
preferred product is the alkene that has the
2. During elimination reaction sp3 carbon
greater number of alkyl groups attached to
atom changes to sp2 carbon atom.
doubly bonded carbon atoms.
The ease of dehydrohalogenation of alkyl
Some elimination reactions useful to prepare halides accordingly is in the order 30 > 20 > 10
alkenes are described below. The ease of formation of alkenes :
i. Dehydrohalogenation of alkyl halides R2C = CR2 > R2C= CHR > R2C = CH2,
Dehydrohalogenation means removal of RCH=CHR > RCH=CH2
hydrogen (H) atom and halogen (X) atom from The stability of alkenes :
adjacent carbon atoms. The carbon carrying X R2C = CR2 > R2C= CHR > R2C = CH2,
is called a-carbon atom. RCH=CHR > RCH=CH2 > CH2 = CH2
240
 Can you recall? Can you tell?

• What are alcohols ? 1. Explain by writing a reaction, the main

• What is a dehydration reaction? product formed on heating 2-methylbutan-
• What is a catalyst ? 2-ol with concentrated sulphuric acid.
2. Will the main product in the above
reaction show geometrical isomerism?
ii. Dehydration of alcohols : Alcohols on
heating with sulphuric acid form alkenes with
elimination of water molecule. The reaction is iii. By dehalogenation of vicinal dihalides :
known as catalyzed dehydration of alcohols. Removal of two halogen atoms from
The exact conditions of dehydration depend adjacent carbon atoms is called dehalogenation.
upon the alcohol. The dihalides of alkane in which two halogen
Dehydration of alcohol is an example of atoms are attached to adjacent carbon atoms
b-elimination since OH group from a-carbon are called vicinal dihalides. Vicinal dihalides
along with a H atom from b-carbon atom is on heating with zinc metal form alkenes.
removed. C C + Zn C C + ZnX2
β α conc. H2SO4
C C + X X
C C ∆ Vicinal dihalide Alkene
H OH CH2Br-CH2Br + Zn CH2=CH2+ ZnBr2
H2O
Alcohol Alkene 1,2-Dibromoethane Ethene
The ease of dehydration of alcohols is in the
CH3CHBr - CH2Br + Zn CH3CH = CH2
order 30 > 20 > 10
1,2-Dibromopropane Propene
H H H + ZnBr2
β α 75% H2SO4
H3C - C - C - C - H 413 K (II) Addition reactions : By partial reduction
H H OH of alkynes (or controlled hydrogenation of
H3C - CH2 - CH = CH2 + H2O alkynes) :
Butan-1-ol But-1-ene (main product )
The C ≡ C triple bond of alkynes can be
H H H partially reduced to a C = C double bond with
β α β 60% H2SO4 calculated quantity of dihydrogen in presence
H3C − C − C − C − H 373K
of Lindlar's catalyst (palladised charcoal
H OH H
deactivated partially with quinoline or sulfur
H3C - CH2 = CH - CH3 + H3C - CH2 - CH = CH2 compound). The Cis isomer is obtained by this
(major) (minor) + H2O
method.
R R
Pd-C
H H R - C≡C - R + H-H quinoline C =C
β CHβ Alkyne H
β α 3 20% H2SO4 H
cis-Alkene
H−C−C−C−H 363K
H OH H Trans alkene is obtained from alkyne on
2-Methylpropan-2-ol reduction with sodium in liquid ammonia.
CH3 H
R
H3C − C = CH2 + H2O Na
R-C≡C-R liquid NH3 C =C
2-Methylprop-1-ene
Alkyne H R
trans-alkene
241
 Table 15.3 : Melting point and boiling point of alkenes
Fornula Name Molecular mass (u) b.p. (K) m.p. (K)
CH2=CH2 Ethene 28 171 104
CH2 = CHCH3 Propene 42 225 88
CH2 =CHCH2CH3 But-1-ene 56 267 --
CH2 = CH(CH2)2CH3 Pent-1-ene 70 303 --
CH2 =CH(CH2)3CH3 Hex-1-ene 84 337 135
cis CH3CH = CH CH3 cis-But-2-ene 56 277 134
trans CH3CH = CHCH3 trans-But-2-ene 56 274 167
CH2 = C(CH3)2 Isobutylene 56 266 132

15.2.3 Physical properties of alkenes : Alkenes H H

H H
are nonpolar or weakly polar compounds those CCl
H3C C C H + Br2 room temp H3C C C H
4

are insoluble in water, and soluble in non- Br Br

polar solvents like benzene, ether, chloroform. Propene red brown 1,2- Dibromopropane
They are less dense than water. From Table (Colourless)
15.3, it is clear that the boiling point of alkene Addition of bromine is useful test for
rises with increasing number of carbons. detection C = C in unknown compounds. Red
Branched alkenes have lower boiling point brown colour of bromine rapidly disappears in
than the corresponding straight chain alkane. carbontetrachloride solution if a C = C double
The boiling point of alkene is very nearly the bond is present in the compound.
same as that of alkane with the same carbon 3. Addition of hydrogen halides/
skeleton. hydrohalogenation : Addition of hydrogen
15.2.4 Chemical properties of alkenes : halides (HX) like hydrogen chloride, hydrogen
Alkenes are more reactive than alkene bromide and hydrogen iodide converts alkene
due to the presence of pi (p) electrons. They into the corresponding alkyl halides.
undergo electrophilic addition reactions. The
different reactions of alkenes are given below:
1. Addition of dihydrogen/hydrogenation ( see C C +H−X C C
section 15.1.4). H X
Alkene Hydrogen halide Alkyl halide
2. Addition of halogens/halogenation.
Alkenes are converted into the corresponding
vicinal dihalides by addition of halogens The order of reactivity of hydrogen
(X2 = Cl2 or Br2) . halides is HI > HBr > HCl
Addition reaction of HBr to symmetrical
alkenes : The addition of HBr to symmetrical
CCl4
C C + X2 room temp
C C alkenes yield only one product.
X X
Alkene Vicinal dihalide H2C = CH2 + H − Br H3C − CH2 − Br
Ethene Bromoethane
Iodine generally fails to react. H2C = CH2 + H − Br Br − CH2 − CH3
Ethene Bromoethane
H H
H H
CCl4
H C C H + Cl2 room temp H C C H
Cl Cl
Ethene 1,2-Dichloroethane
242
Addition reaction of HBr to unsymmetrical
alkenes : Addition of HBr to unsymmetrical Remember
alkenes yield two isomeric products.
H3C - CH2 - CH2 - Br 1. The orientation of addition of HBr to
1-Bromopropane
A unsymmetrical alkene is determined by
(minor)
the presence or absence of peroxide.
H3C - CH = CH2 + H - Br
Propene 2. The peroxide has no effect upon the
B 2-Bromopropane addition of HCl and HI.
(major)
H3C − CH − CH3
4. Addition of sulfuric acid
Br Alkenes react with cold concentrated
Experimentally it has been found that sulphuric acid to form alkyl hydrogen sulfate
2-Bromopropane is the major product. ( ROSO3H). The addition takes place according
Russian chemist Markovnikov studied to Markovnikov's rule.
hydrohalogenation of a number of an
unsymmetrical alkenes and formulated a C C +H OSO3H
geneneral rule (1869) as follows : Alkene Cold conc.
Markovnikov's rule : When an unsymmetrical
C C
reagent is added to unsymmetrical alkene, the
negative part (X ) of the reagent gets attached H OSO3H
Alkyl hydrogen sulfate
to the carbon atom which carries less number
of hydrogen atoms. H H
Anti- Markovnikov addition Or peroxide H C C H +H OSO3H
effect or Kharasch - Mayo effect : In 1933, ethene Cold conc.
M. S. Kharasch and F. R. Mayo discovered that H H
the addition of HBr to unsymmetrical alkene
in the presence of organic peroxide (R-O-O-R) H C C H
takes place in the opposite orientation to that H OSO3H
suggested by Markovnikov 's rule. ethyl hydrogen sulfate
(C6H5CO)2 O2
CH3 - CH = CH2 + H2SO4 CH3 - CH - CH3
H3C − CH = CH2 + H − Br Benzoyl peroxide OSO3H
Propene
isopropyl hydrogen sulfate
H3C − CH2 − CH2 − Br If alkyl hydrogen sulfate is diluted with
1-Bromopropane
water and heated, then an alcohol having the
CH3 same alkyl group as the original alkyl hydrogen
(C H CO) O sulfate is obtained. This is an excellent method
H3C − C = CH2+ H − Br Benzoyl peroxide
6 5 2 2

2-Methylprop-1-ene for the large scale manufacture of alcohols.
CH3
H3C − C − CH2 − Br H - OH
CH3 - CH2 - OSO3H
H ∆
1-Bromo-2-methylpropane Ethyl hydrogen sulfate
H H
H C C H + H2SO4
Internet my friend
H OH
https://www.britanicacom>science>hydrocarbon Ethanol

243
 H H O
H H
H H H H
O3
H C C CCl4 H C C H
H3C − C − CH3
H - OH O O
∆ H C C CH3
OSO3H H OH
(Ethene) (Ethene ozonide)
Isopropyl hydrogen sulphate propan-2-ol H H
H2O
+ H2SO4 Zn dust C=O+O=C + ZnO
Reactive alkenes on adding water H H
molecules in the presence of concentrated
sulphuric acid, form alcohol.The addition of (Formaldehyde) (Formaldehyde)
water takes place according to Markovnikov's H H O
H H
rule.This reaction is known as hydration of H3C C C H O3
H3C C C H
1 2 CCl4 1 O O2
alkenes.
CH3H (Propene) (Propene ozonide)
H + H − OH
H+
H3C H
H3C C C H2O
2-Methylprop-1-ene Zn dust C = O + O =2C + ZnO
1 H
CH3 H
(Acetaldehyde) (Formaldehyde)
H3C − C − CH3
OH
2-Methylpropan-2-ol Remember
Can you tell? 1. In the cleavage products a carbonyl group
( C =O) is formed at each of the original
Why are Propan-1-ol and 2-Methypropan-1-
doubly bonded carbon atoms.
ol are not prepared by this method ?
2. Knowing the number and arrangement
of carbon atoms in these aldehydes and
5. Ozonolysis of alkenes : The C = C double ketones produced, we can identify the
bond gets cleaved on reaction with ozone structure of original alkene.
followed by reduction. This overall process of 3. The role of zinc dust is to prevent the
formation of ozonide by reaction of ozone with formation of hydrogen peroxide which
alkene in the first step and then decomposing oxidizes aldehydes to corresponding
it to the carbonyl compounds by reduction in acids.
the second step is called ozonolysis. 4.This reaction is used to locate the position
O
O HO and determine the number of double
C C CCl
3
C C 2

1 2 O
4 O Zn dust
bonds in alkenes.
Alkene alkene ozonide

1 2 Use your brain power

C = O + O = C + ZnO
On ozonolysis an alkene forms the
Carbonyl compounds following carbonyl compounds. Draw the
Ozone gas is passed into solution of structure of unknown alkene from which
the alkene in an inert solvent like carbon these compounds are formed.
tetrachloride, unstable alkene ozonide is HCHO and CH3COCH2CH3
obtained. This is subsequently treated with
6. Hydroboration- oxidation of alkene
water in the presence of a reducing agent zinc
Alkenes with diborane in tetrahydrofuran
dust to form carbonyl comounds, namely,
(THF) solvent undergo hydroboration to
aldehydes and/or ketones .
form trialkylborane, which on oxidation with
244
alkaline peroxide forms primary alcohol. The H HO Heat, pressure
overall reaction gives Anti-Markovnikov's n C=C 2
polymerization
product from unsymmetrical alkenes H H
(Ethene) H H H H
6( C C ( + (BH3)2 THF 2 ( C C ( 3
B

(Monomer)
C−C−C−C
H H H H
(Alkene) (Diborane) (Trialkylborane) H H
HO - OH
OH + C C
OH
+B(OH)3 Or ( ( C−C
H H
n

(Alcohol) (Polyethene)
(Polymer)
H
6H C
H
C H+
( (H
H B
H 2
THE
solvent 2(CH3- CH2-)3B
Here n represents the number of repeating units
and is a large number.

(Ethene) (Diborane)
Use your brain power

2
( H3C - CH2
H3C - CH2
H3C - CH2
( B
3 HO-OH
NaOH
Write the structure of monomer from
which each of the following polymers are
obtained.
a. Teflon (CF2 − CF2)
(Triethylborane)
H

( (
+6CH3-CH2-OH + 2B(OH)3 CH3
(Ethanol) b. Polypropene C−C
n

( (
H Cl
H H H H H

( (
THE
6H C C
3
C H+ H B solvent
H 2 c. Polyvinyl chloride C−C
(Propene) (Diborane) n
H Cl

( (
2(CH3-CH2- CH2-)3B
H3C - CH2 - CH2 8. Hydroxylation : Alkenes react with cold
3 HO-OH
H3C - CH2 - CH2 B NaOH and dilute alkaline potassium permanganate
H3C - CH2 - CH2 to form glycols.
(Tri-n-propylborane) H H
3CH3−CH2−CH2− OH + B(OH)3 C = C + H - OH + (O) KMnO
alkaline

(Propan-1-ol) H H
4

7. Polymerization : The process in which (Ethene)

large number of small molecules join together H H
and form very large molecules with repeating H C C H
units is called polymerization. The compound OH OH
having very large molecules made of large (Ethane-1,2-diol)
number repeating small units is called polymer H3C H
alkaline
and the simple compound forming the repeating C=C + H − OH + (O) KMnO4
units in the polymer is called monomer. H H H H
For example, ethene at high temperature and (Propene) H3C C C H
under high presssure interacts with oxygen,
OH OH
and undergoes polymerization giving high (Propane-1,2-diol)
molecular weight polymer called polyethene.
245
 Hydroxylation of alkenes is the most Table 15.4 : Lower alkynes
important method for the synthesis of 1,2-diols n Molecular Structural formula IUPAC
and
(Glycols). During this reaction the purple formula
Common name
name
colour of KMnO4 disappears. Hence such 2 C2H2 H-C ≡ C-H Ethyne
reaction serves as qualitative test for detecting Acetylene
the presence of double bond in the compound 3 C3H4 CH3-C≡ CH Methyl Propyne
under test. This is known as Baeyer's test. acetylene
9. Oxidation : Alkenes on oxidation with 4 C4H6 CH3-CH2-C≡CH But-1-yne
acidic KMnO4 or acidic potassium dichromate Ethyl acetylene
form ketones and / or acids. 5 C4H6 C H 3 - C ≡ C - C H 3 But-2-yne
O
KMnO , H⊕ Dimethyl acetylene
H3C − CH = CH2 4
(O) H3C - C - OH
(Prop-1-ene) (Ethanoic acid)
+ CO2 + H2O Do you know ?
CH3
KMnO4, H⊕
H3C - C = CH - CH3 (O) 1. Simplest alkyne is ethyne which is known
(2-Methylbut-2-ene) as acetylene.
CH3 O
H3C - C = O+ H3C − C − OH 2. The carbon-carbon triple bond is a
Propan-2-one Ethanoic acid functional group.
15.2.5 Uses of alkenes
3. The aliphatic unsaturated hydrocarbons
1. Alkenes, are used as starting materials for
containing two or three carbon-carbon triple
preparation of alkyl halides, alcohols,
aldehydes, ketones , acids etc. bonds are called alkadiynes and alkatriynes,
2. Ethene and propene are used to manufacture respectively.
polythene, polypropylene those find use in 4. Cicutoxin from poisonous plants 'water
bags, toys, bottles, etc. hemlock'.
3. Ethene is used for artificial ripening of
fruits, such as mangoes. HO - (CH2)3 - C ≡ C - C ≡ C - (C10H14) -OH

Can you tell? 15.3.2 Preparation of alkynes

• What are aliphatic hydrocarbons? a. Industrial sources :
• Compare the proportion of carbon i. Ethyne is industrially prepared by controlled,
and hydrogen atoms in ethane, ethene high temperature partial oxidation of methane.
1773K
and ethyne. Which compound is most 6CH4 + 2O2 2H - C ≡ C - H + 2 CO2 + 10 H2
unsaturated with hydrogen ? Methane Ethyne
ii. From calcium carbide : Industrially the
15.3 Alkynes : Alkynes are aliphatic alkyne ethyne is prepared by reaction of
unsaturated hydrocarbons containing at least calcium carbide with water.
one C ≡ C.The number of hydrogen atoms is
CaC2 + 2H2O C2H2 + Ca (OH)2
still less in alkynes as compared to alkenes.
Their general formula is CnH2n-2 . Table 15.4
shows names and formulae of lower alkynes.
15.3 Isomerism in alkynes : Alkynes show
position isomerism which is a type of structural
isomerism. For example 1-butyne and
2-butyne. 1-Alkynes are also called terminal
alkynes.
246
b. Methods of preparation of alkynes H−C≡C−H
1. By dehydrohalogenation of vicinal R−C≡C−H
dihalides : Removal of H and X from adjacent Such hydrogen atom shows appreciable
carbon atoms is called dehydrohalogenation. acidity and can be given away as proton on
Vicinal dihalides react with alcoholic solution reaction with sufficiently strong base.
of potassium hydroxide to form alkenyl halide In this method a smaller terminal alkyne first
which on further treating with sodamide forms reacts with a very strong base like lithium
alkyne. amide to form metal acetylide (Lithium amide
H H is easier to handle than sodamide).
C C + KOH Higher alkynes are obtained by reacting
- KX
- H2O metal acetylides (alkyn-1-yl lithium) with
X X primary alkyl halides.
Vicinal dihalide (Alcoholic)
H R - C ≡ C - H +Li+ NH2- R - C ≡ C - Li + NH3
Na NH2
+ -

C C X - NaX -C≡C- Terminal alkyne Lithium amide Alkyn-1-yl lithium

- NH3
Alkenyl halide alkyne R - C ≡ C - Li + R1 - X R - C ≡ C-R1 + LiX
H H Alkyn-1-yl lithium Primary alkyl halide Higher alkyne

H C C H + KOH - KBr Li+NH2- H3C − CH2 − Br

(Alcoholic) - H 2O H-C≡C-H H - C ≡ C - Li
Br Br -NH3 Bromoethane
1,2-Dibromoethane Ethyne Ethynyllithium
H H
Na+ NH2- H - C ≡ C - CH2 - CH3 + LiBr
H C C Br - NaX H-C≡C-H But-1-yne
- NH3
Bromoethene Ethyne Li+NH2-
H3C - C ≡ C - H -NH3
H3C - C ≡ C - Li
H H Propyne Prop-1-yn-1-yl lithium

H3C C C H + KOH - KCl

H3C − CH2 − Br
H3C - C ≡ C - CH2 - CH3 + LiBr
- H2O Bromoethane
Cl Cl (Alcoholic) Pent-2-yne
1,2-Dichloropropane

H H
Na+ NH2- Use your brain power
H3C C C Cl - NaCl H3C - C ≡ C - H
- NH3
1-Chloropropanene Propyne Convert : 1-Bromobutane to Hex-1yne.

Can you tell? 15.3.3 Physical properties of alkynes : The

physical propeties of alkynes are similar to
Why sodamide is used in second step those of alkanes and alkenes. They are less
to remove HX from alkenyl halide in place dense than water. They are insoluble in water
of alcoholic KOH? and quite soluble in less polar organic solvents
like ether, benzene, carbon tetrachloride. The
2. From terminal alkynes : Terminal alkynes melting points and boiling points of alkynes
are the compounds in which hydrogen atom is increase with an increase in molecular mass
directly attached to triply bonded carbon atom. (Table 15.5).

247
 Table 15.5 : Melting point and Boiling point of alkynes
Fornula Name Molecular Physical b.p.(K) m.p.(K)
mass/u State
CH =CH Ethyne 26 Gas 198 191
CH = CCH3 Propyne 40 Gas 250 171.5
CH =CCH2CH3 But-1-yne 54 Gas 282 151
CH = C(CH2)2CH3 Pent-1-yne 68 Liquid 313 175
CH =C(CH2)3CH3 Hex-1-yne 82 Liquid 345 149

15.3.4 Chemical properties of alkynes :

1. Acidity of alkynes : Use your brain power
The hydrogen bonded to C ≡ C triple Arrange following hydrocarbons in the
bond has acidic character. Lithium amide ( increasing order of acidic character.
LiNH2) is very strong base and it reacts with propane, propyne, propene.
terminal alkynes to form lithium acetylides
with the liberation of hydrogen indicating
acidic nature of terminal alkynes. Why is Do you know ?
it so ? In terminal alkynes, hydrogen atom Acidic alkynes react with certain
is directly attached to sp hybridized carbon heavy metal ions like Ag+ and Cu+ and form
atom. In sp hybrid orbital, the percentage of insoluble acetylides. On addition of acidic
s- character is 50%. An electron in s-orbital is alkyne to solution of AgNO3 in alcohol
very close to the nucleus and is held tightly. form a precipitate which indicates that the
The sp hybrid carbon atom in terminal alkynes hydrogen atom is attached to triply bonded
is more electronegative than the sp2 carbon in carbon. This reaction is used to differentiate
ethene or the sp3 carbon in ethane. Due to high terminal alkynes and non-terminal alkynes.
electronegative character of carbon in terminal 2. Addition of dihydrogen (See method of
alkynes, hydrogen atom can be given away as preparation of alkenes from unsaturated
proton ( H+ ) to very strong base. hydrocarbons)
Examples 3. Addition of halogens
CCl
Li+NH2- -C≡C-+X-X 4
-C=C-
H−C≡C−H -NH3 H − C ≡ C − Li
Ethyne Monolithium ethynide X X
Li+NH2-
Li − C ≡ C − Li + NH3 Alkyne (X2 = Cl2, Br2) 1, 2 - Dihaloalkene
Dilithium ethynide X X
Li+NH2-
H3C - C ≡ C - H H3C - C ≡ C - Li X− X
-NH3 −C−C−
Prop-1-yne Lithium propynide
X X
The relative acidity of alkanes, alkenes and 1, 1, 2, 2 - Tetrahalokane
alkynes follows the order Ethyne reacts with bromine in inert solvent
H − C ≡ C − H > H2C = CH2 > H3C − CH3 such as carbon tetrachloride to give
tetrabromoethane.
H - C ≡ C - H + Br - Br CCl 4

Ethyne Bromine Br Br
Can you tell?
Br − Br
Alkanes and alkenes do not react H-C=C- H H −C-C−H
with lithium amide. Give reason. Br Br Br Br
1,2-Bibromoethene 1,1,2,2-Tetrabromoethane

248
 Red-brown colour of solution of bromine Alkynes react with water in presence of
in carbon tetrachloride disappears. This 40% sulphuric acid and 1% mercuric sulphate
test can be used to detect the presence of to form aldehydes or ketones i.e. carbonyl
unsaturation in given compound. compounds.
4. Addition of hydrogen halides
40% H2SO4
−C≡C−+H−X −C=C− H − C ≡ C − H + H − OH 1% HgSO4

[ [
Ethyne
H X H
Alkyne (HX = HCl , HBr,HI) Tautomerisation
H C C H
H X
H− X
O H
−C-C−
Vinyl alcohol H
H X
Geminal dihalides H − C − C− H
O H
Hydrogen halides (HCl, HBr and HI) add
Ethanal
to alkynes across carbon-carbon triple bond in
40% H2SO4
two steps to form geminal dihalides (in which H3C − C ≡ C − H + H − OH 1% HgSO4
two halogen atoms are attached to the same Propyne

[ [
carbon atom).The addition of HX in both the H
steps takes place according to Markovnikov's H3C C C H Tautomerisation
rule.
H − C ≡ C − H + H − Br O H
H − C = C −H
H Br H3C − C − CH3
Ethyne Hydrogen bromide 1-Bromoethene O
H Br Propanone
H − Br
H −C-C−H Use your brain power
H Br
1,1-Dibromoethane50% Convert : 3-Methylbut-1-yne into
3-Methylbutan-2-one.
H3C − C ≡ C − H + H−Br H 3C − C = C − H
15.3.5 Uses of acetylene :
Br H 1. Ethyne (acetylene) is used in preparation of
Propyne Hydrogen bromide 2-Bromopropene Ethanal (acetaldehyde), Propanone (acetone),
Br ethanoic acid (acetic acid).
H − Br
H3C − C − CH3 2. It is used in the manufacture of polymers,
Br synthetic rubber, synthetic fibre, plastic etc.
2,2-Dibromopropane 3. For artificial ripening of fruits.
The order of reactivity of hydrogen halides is 4. In oxy-acetylene ( mixture of oxygen and
HI > HBr > HCl acetylene) flame for welding and cutting of
5. Addition of water

[ [
metals.
40% H SO C C
- C ≡ C - + H - OH 1% HgSO
2 4
15.4 Aromatic Hydrocarbons :
4H OH
Alkyne Unstable Can you recall?
H
Tautomerism • What are aromatic hydrocarbons?
− C − C−
• What are benzenoid and non-benzenoid
H O
Carbonyl compound aromatics ?
249
 Many organic compounds obtained
from natural sources like resins, balsams, Remember
oil of wintergreen, etc. possessing pleasant
fragrance (aroma = smell) are named as 1. Aromatic compounds contain planar
aromatic compounds. Aromatic hydrocarbons cyclic rings.
(also called arenes) contain only carbon and 2. Not all compounds those resemble
hydrogen. Benzene is the simplest aromatic benzene have pleasant odour (smell).
compound.
Anthracene is
Benzene and all compounds that have
odourless.
structures and chemical properties resembling
3. Many compounds having pleasant odour
benzene are classified as aromatic compounds.
do not resemble benzene.
Examples are :
CH3 Br O
H 3C C O CH3
(Methyl acetate)

(Benzene) (Methylbenzene) (Bromobenzene) O

H3C C O C2H5
OH (Ethyl acetate)
Cl
H C Cl
(Phenol) (Naphthalene) Cl
15.4.1 Benzene : The molecular formula of (Trichloromethane or chloroform)
benzene is C6H6. Benzene is parent compound
It is a colourless liquid having characteristic
of most of the aromatic compounds.
odour. Its boiling point is 353K.
Coal-tar and petroleum are the two
It was synthesized by Berthelot (1870)
large-scale sources of benzene (and aromatic
from acetylene. Benzene was originally called
compounds like toulene , phenol, naphthalene.).
phene and hence C6H5 is called phenyl group.
Table 15.6 : Difference between aromatic and aliphatic compounds
Aromatic compounds Aliphatic compounds
1. Aromatic compounds contain higher 1. Aliphatic compounds contain lower
percentage of carbon. percentage of carbon.
2. They burn with sooty flame. 2. They burn with non-sooty flame.
3. They are cyclic compounds with alternate 3. They are open chain compounds.
single and double bonds.
4. They are not attacked by normal oxidizing 4. They are easily attacked by oxidizing and
and reducing agents. reducing agents.
5. They do not undergo addition reactions 5. Unsaturated aliphatic compounds undergo
easily. They do not decolourise dilute alkaline addition reactions easily.They decolourise
aqueous KMnO4 and Br2 in CCl4, though double dilute aqueous alkaline
bonds appear in their structure. KMnO4 and Br2 in CCl4.
6. They prefer substitution reactions. 6. The saturated aliphatic compounds give
substitution reactions.
250
15.4.2 Structure of benzene : H
1. Molcular formula of benzene, C6H6, H C H
C C Usually
indicates the high degree of unsaturation. C C written as
2. Open chain structure NOT possible : Open H C H
chain or cyclic structure having double and H
The Kekulé structure indicates
triple bonds can be written for C6H6. But
the possibility of two isomeric
benzene does not behave like alkenes or
1,2-dibromobenzenes. In one of the isomers,
alkynes (see Table 15.7). This indicates that
the bromine atoms would be attached to the
benzene can not have the open chain structure.
doubly bonded carbon atoms whereas in the
Table 15.7 : Comparative reactivity of alkenes
other, they would be attached to single bonded
and benzene
carbons.
Reaction Alkene Benzene
Br Br
With dil. Decolourisation No Br Br
alka. of purple colour of decolourisation +
KMnO4 KMnO4 However, benzene was found to form only
With Br2 in Decolourisation of No one ortho-disubstituted benzene. This problem
CCl4 red brown decolourisation was overcome by Kekule' by suggesting the
colour of bromine concept of oscillating nature of double bonds
With H2O Addition of H2O No reaction in benzene as given below.
in acidic molecule
medium

3. Evidence of cyclic structure : Benzene yields Even with this modification, Kekule' structure
only one and no isomeric monosubstituted of benzene failed to explain unusual stability
bromobenzene (C6H5Br) when treated with and preference to substitution reactions rather
equimolar bromine in FeBr3. This indicates than addition reactions, which was later
that all the six hydrogen atoms in benzene are explained by resonance.
identical. 5. Stability of benzene:
FeBr3
C6H6 + Br2 C6H5Br + HBr Benzene is a hybrid of various resonance
srtuctures.The two structures, A and B given
This is possible only if benzene has cyclic
by Kekulé are the main contributing structures.
structure of six carbons bound to one hydrogen
The resonance hybrid is represented by
atom each.
inserting a circle or a dotted circle inscribed
Benzene on catalytic hydrogenation gives
in the hexagon as shown in (C). The circle
cyclohexane.
Ni represents six electrons delocalized over the
C6H6 + 3H2 C6H12
∆ six carbon atoms of benzene ring.
(Benzene) (Cyclohexane)
This confirms the cyclic structure of benzene Or
and three C = C in it.
4. Kekulé structure of benzene : (A) (B) (C)
August Kekulé in 1865 suggested the A double headed arrow between the
structure for benzene having a cyclic planar resonance structures is used to represent the
ring of six carbon atoms with alternate single resonance phenomenon.
and double bonds and hydrogen atom attached Stability of benzene : The actual molecule is
to each carbon atom. more stable than any of its resonance structures.
For benzene, the stability due to resonance

251
is so high that p-bonds of the molecule resist atom energies.
breaking. This explains lack of reactivity of P-orbital π MO
benzene towards addition.
The orbital overlap gives us better picture
of structure of benzene. All six carbon atoms
in benzene are sp2 hybridised. Two sp2 hybrid
orbitals of carbons overlap and form carbon-
carbon sigma (s) bond and the remaining third
sp2 hybrid orbital of each carbon overlaps with Fig 15.6 : Representative p molecular
s orbital of a hydrogen atom to form six C-H orbital in benzene
sigma bonds.
Hσ σ σ H Remember
σ

H
σ σ
H In benzene , a. All carbon and hydrogen
atoms lie in the same plane.
σ

σ σ σ b. Six sigma ( s ) bonds lie in the same

H H
plane.
The unhybrid p orbitals of carbon atoms c. All bond angles are 1200
overlap laterally forming p bonds. There are H H
two possibilities of forming three p bonds by
overlap of p orbitals of C1-C2, C3-C4, C5-C6 or
120°
C2-C3, C4-C5, C6-C1, respectively, as shown in H 120° H
Fig. 15.5; both are equally probable. According
to resonance theory (Chapter 5) these are two
resonance structures of benzene.
H H
1 2
The six electrons of the p orbitals cover
6 3 all the six carbon atoms and are said to be
Or
delocalized. Delocalization of p electrons
5 4 results in stablity of benzene molecule.
6. Bond parameters of benzene : X-ray
diffraction data indicate that all C-C bond
lengths in benzene are equal ( 139 pm) which
is an intermediate between C-C (154 pm)
Or and C=C bond (133pm). Thus absence of
pure double bond in benzene accounts for its
reluctance to addition reactions under normal
conditions, which explains unusual behaviour
Fig. 15.5 Overlap of p orbitals in benzene of benzene (Refer to sec.14.6.5).
According to molecular orbital (MO)
theory (Chapter 5) the six p orbitals of six
carbons give rise to six molecular orbitals of C C
benzene. Shape of the most stable MO is as C C
shown in Fig. 15.6. 1.54 A° 1.39 A°
Three of these p molecular orbitals lie Single-bond lenght Benzene-bond length
above and the other below those of free carbon

252
 4n + 2 = 6, ∴ 4n = 6-2 =4
C C n = 4/4 = 1, Here 'n' comes out to be an integer.
Hence benzene is aromatic.
1.34 A°
2. Naphthalene : It is cyclic and planar. It
Double-bond length has 5 double bonds and 10 p electrons.It has
15.4.3 Aromatic character ( Huckel Rule) : p orbital on each carbon atom of the ring.
Benzene undergoes substitution reaction Hence a continuous overlap around the ring is
rather than addition reactions. This property posssible. This is in accordance with Huckel
is common to all aromatic compounds and rule.
is referred to as aromaticity or aromatic 4n + 2 = Number of p electrons
character. The aromatic character of benzene 4n + 2 = 10, ∴ 4n = 10 -2 = 8
is correlated to its structure. n = 8/4 = 2, Here 'n' comes out to be an integer.
Aromaticity is due to extensive cyclic Hence napthalene is aromatic.
delocalization of p electrons in planar ring 3. Pyridine : Pyridine has three double bonds
structures. and 6 p electrons. The six p orbital containing
The following three rules of aromaticity six electrons form delocalized p molecular
are useful in predicting whether a particular orbital. The unused sp2 hybrid orbital of
compound is nitrogen containing two non-bonding electrons
aromatic or non-aromatic. is as it is.
1. Aromatic compounds are cyclic and planar
(all atoms in ring are sp2 hybridized).
N
2. Each atom in aromatic ring has a p-orbital.
The p-orbitals must be parallel so that
Non bonding
continuous overlap is possible around the ring.
electron pair
3. Huckel Rule : The cyclic p molecular
orbital formed by overlap of p-orbitals must 4n + 2 = Number of p electrons
contain ( 4n + 2) p electrons, where n= integer 4n + 2 = 6, ∴ 4n = 6 -2 = 4
0,1,2,3 ...etc. n = 4/4 = 1, Here 'n' comes out to be an integer.
Let us apply these rules to the following Hence pyridine is aromatic.
compounds 4. Cycloheptatriene : It is cyclic and planar. It
has three double bonds and 6 p electrons. But
one of the carbons is saturated (sp3 hybridized)
and does not possess a p orbital. Hence a
Benzene Naphthalene
continuous overlap around the ring is not
1. Benzene : It is cyclic and planar. It has possible.Therefore, it is non- aromatic.
three double bonds and six p electrons. It has
a p orbital on each carbon of the hexagonal sp3 hybridized
ring. Hence a continuous overlap above and
below the ring is posssible. 15.4.4 Preparation of aromatic compounds
a. Industrial source of aromatic compounds
Coal tar and petroleum are major sources of
aromatic compounds.
b. Methods of preparation of benzene
1. From ethyne ( By trimerization) : Alkynes
when passed through a red hot iron tube at 873
This compound is aromatic, 4n + 2 = Number
K, polymerize to form aromatic hydrocarbons.
of p electrons.
253
Ethyne when passed through a red hot iron to give benzene hexachloride .
tube at 873 K undergoes trimerization to form H
Cl H Cl H
benzene. H H
H C C C
CH UV light
+ 3Cl2 Cl
CH
H Cl C C H
CH H
Red hot iron tube H C
Or H Cl
CH Cl H
873k
CH Benzene Benzene hexachloride (BHC)
g - isomer of benzene hexachloride is called
CH

Can you recall? gammexane or lindane which is used as

insecticide.
What is decarboxylation ? ii. Addition of hydrogen : When a mixture
2.From sodium benzoate : of benzene and hydrogen gas is passed
(By decarboxylation) over heated catalyst nickel at 453 K to 473
When anhydrous sodium benzoate is heated K,cylohexane is formed.
with soda-lime it gives benzene. + 3H2
Ni
O 453 - 473 K
C ONa
Benzene (C6H6) Cyclohexane
CaO (C6H12)
+ NaOH ∆ +Na2CO3 iii. Addition of ozone : When benzene is treated
Sodium benzoate Benzene with ozone in presence of an inert solvent
3. From phenol ( By reduction) : When carbon tetrachloride, benzene triozonide is
vapours of phenol are passed over heated zinc formed which is then decomposed by zinc dust
dust, it gives benzene. and water to give glyoxal.
H O
OH C O
H
CO C H
+ Zn ∆ + ZnO + 3O3 O O
C H
Phenol Benzene O C O
O
H C O
15.4.5 Physical properties of benzene
1. Benzene is colourless liquid. H
Benzene
2. Its boiling point is 353K and melting point CHO

is 278.5 K. Zn / H2O
3 + 3H2O2
3. It is isoluble in water. It forms upper layer CHO
when mixed with water.
Ethanedial or glyoxal
4. It is soluble in alcohol, ether, and chloroform.
II. Substitution reactions : Benzene shows
5. Benzene vapours are highly toxic which on
electrophilic substitution reactions, in which
inhalation lead to unconsciousness.
one or more hydrogen atoms of benzene ring
15.4.6 Chemical properties of benzene
are replaced by electrophilic groups like -Cl,
Aromatic compounds are characterised by
-Br, -NO2, -SO3H, -R (alkyl group) , -COR
electrophilic substitution reactions. However,
(Acyl group) etc. (see Chapter 14).
they undergo addition and oxidation reactions
i. Halogenation : In this reaction, hydrogen
under special conditions. Some reactions of
atom of benzene ring is replaced by halogen
benzene are discussed below.
atom .
I. Addition reactions
i. Addition of chlorine : Benzene when treated
with chlorine in presence of bright sunlight or
UV light, adds up three molecules of chlorine
254
Chlorination NO2
Cl H H
Fe + H2O
+ Cl2 + HCl H H
in dark
H
Benzene Chlorobenzene
Nitrobenzene
Chlorine reacts with benzene in dark in the
presence of iron or ferric chloride or anhydous When benzene is heated with a mixture
aluminium chloride or red phosphorous as of concentrated nitric acid and concentrated
catalyst to give chlorobenze . sulfuric acid (nitrating mixture) at about
Electrophile : Cl⊕ , Chloronium ion 313 K to 333 K , it gives nitrobenzene.
Formation of the electrophile : Electrophile : NO2 ⊕ , nitronium ion.
Cl Cl + FeCl3 Cl⊕ + [FeCl4] Formation of the electrophile : HO NO2 +
2H2SO4 2HSO4 + H3O⊕ + NO2⊕
Bromination of benzene is similar to
iii. Sulfonation :
chlorination : H
Br H H fumimg H2SO4
+ HO -SO3H
FeBr3 373 K
H H
+ Br2 + HBr
H
Benzene Bromobenzene Benzene
SO3H
Electrophile : Br⊕, H H
Formation of electrophile : + H2O
Br Br + FeBr3 Br⊕ + [FeBr4] H H
Iodination of benzene is not possible as it is H
reversible process. Benzenesulfonic acid
With excess of chlorine, benzene gives When benzene is heated with fuming
hexachlorobenzene. sulfuric acid (oleum) at 373 K, it gives benzene
H sulfonic acid.
H H anhy.AlCl3 Electrophile : SO3 , free sulfur trioxide
+ 6 Cl2 Formation of the electrophile :
H H
2H2SO4 H3O⊕ + HSO4 + SO3
H
iv. Friedel-Craft's alkylation reaction :
Benzene
anhydrous AlCl3
Cl + CH3 - Cl
Cl Cl Methyl Chloride
+ 6 HCl Benzene
Cl Cl CH3
Cl
Hexaclorobenzene + HCl
ii. Nitration :
H Methylbenzene
(Toluene)
H H
Conc. H2SO4 When benzene is treated with an alkyl
+ HO-NO2
H H Heat halide like methyl chloride in the presence
Conc.
H of anhydrous aluminium chloride, it gives
Benzene toluene.
255
The reaction is used to extend the chain outside In benzene, all hydrogen atoms are equivalent.
the benzene ring. Therefore, only one product is possible when it
Electrophile : R⊕ undergoes electrophilic substitution reactions.
Formation of the electrophile : Monosubstituted benzene :
R Cl + AlCl3 R⊕ + AlCl4 substituent
H S
v. Friedel-Craft's acylation reaction : 1
H C H H 6 C 2 H
C C -H C C
anhy. AlCl3 3
+ CH3- CO Cl C C +S C C
heat H C H H 5 C4 H
Acetyl Chloride H H
Benzene Monosubstituted benzene
COCH3 Positions of carbon atoms in mono substituted
benzene :
+ HCl The positions 2 and 6 are equivalent and give
ortho (o-) products.
1- Phenylethanone or Acetophenone The position 3 and 5 are equivalent and give
anhy. AlCl3 meta (m-) products.
+ (CH3- CO)2O heat The position 4 is unique and and gives para
Acetic anhydride (p-) product.
Benzene
Now in benzene , five positions are available
COCH3
for electrophilic substitution.
When monosubstituted benzene is
+ CH3COOH
subjected to further electrophilic substitution,
1- Phenylethanone or Acetophenone
the second substituent i.e. electrophile (see
Chapter 14) or incoming group (E) can
When benzene is heated with an acyl occupy any of these positions and give three
halide or acid anhydride in the presence disubstituted products. But these products are
of anhydrous aluminium chloride, it gives
not formed in equal amounts.
corresponding acyl benzene.
S S
Electrophile : R-C⊕=O acylium ion
Formation of the electrophile : R COCl + E E
AlCl3 R-C⊕ =O + AlCl4
ortho-product
6. Combustion : When benzene is heated in S S S
air , it burns with sooty flame forming carbon -H
dioxide and water.
E+
C6H6 + 15/2 O2 6 CO2 + 3 H2O EE meta-product
General combustion reaction for any S
hydrocarbon (CxHy) can be represented as
para-product
follows:
CxHy + (x + y/4) O2 x CO2 + y/2 H2O
15.4.7 Directive influence of a functional E
group in monosubstituted benzene Two types of behaviour are observed.
Structure of benzene : a. ortho- and para - products or b. meta-
H products are found as major products :
H C H This behaviour mainly depends on the
C C
nature of the substituent (S) already present
C C in the benzene ring and not on the nature of
H C H
H second substituent (E) i.e. incoming group.

256
Ortho and para directing groups : it has no nonbonding electron pair on the key
atom.This is explained on the basis of special
: :

: :

: :
: :
Cl : , Br : , O H , O CH3 , type of resonance called hyperconjugation or
no bond resonance (see Chapter 14).
:

:
NH2 , NHR In case of aryl halides, halogens are
CH3 , C2H5 , R etc. moderately deactivating. Because of their
strong -I effect, overall electron density on
The groups which direct the incoming the benzene ring decreases. It makes the
group to ortho and para positions are called electrophilic substitution difficult. However,
ortho and para directing groups. due to resonance the electron density on
Ortho and para directive influence of -OH ortho and para positions is greater than
group : The resonance theory clearly explains meta positions. Halogens are ortho and para
why certain substituents are ortho/para or meta directing.
directing. Let us study the various resonance Let us study the various resonanting structures
structures of phenol (see Chapter 14). of chlorobenzene.

:
:

O Cl :

:
:

:OH + OH + OH : Cl : O Cl :
: :

:
:

Resonating structures Resonating structures

:

:
:
:

+O H :O H O Cl : : Cl :
: :

It is clear from the above resonance

structures that the ortho and para positions Meta directing and deactivating groups
have a greater electron density than the meta ⊕ O ⊕ H δ⊕ δ
positions. Therefore, -OH group activates N N H C N ,
O , H ,
the benzene ring for the attack of second δ
O
substituent E at these electron -rich centres.
C H,
δ⊕
Remember δ δ
O O
Due to -I effect of -OH group (see
C R C O H
Chapter 14), the electron density on ortho δ⊕ , δ⊕ ,
positions of the benzene ring gets slightly δ
O
reduced. Thus resonance effect and δ⊕
inductive effect of OH group act opposite S O H
etc.
to each other but +R effect of -OH is more O
δ
powerful than -I effect.
All meta directing groups have positive
All ortho and para directing groups
(or partial positive) charge on the atom which
possess nonbonding electron pair on the atom
is directly attached to an aromatic ring.
which is directly attached to aromatic ring.
The groups which direct the incoming
Methyl group is an exception : The only
group to meta positions are called meta
exception to above rule is methyl or alkyl
directing groups.
groups. It is ortho and para directing, although

257
Metadirective influence of -NO2 group can It is clear from the above resonance structures
be explained by resonance theory : Meta that the ortho and para positions have
directing group withdraws electrons from the comparatively less electron density than at
aromatic ring by resonance, making the ring meta positions. Hence, the incoming group/
electron-deficient. Therefore, meta groups are electrophile attacks on meta positions.
ring deactivating groups. Due to -I effect , 15.4.6 Carcinogenicity and Toxicity :
-NO2 group reduces electron density in benzne Benzene is both toxic and carcinogenic
ring on ortho and para positions.So the attack (cancer causing). In fact, it might be considered
of incoming group becomes difficult at ortho "the mother of all carcinogens" as a large
and para positions. Incoming group can attack number of carcinogens have structures those
on meta positions more easily. Let us study the include benzene rings. Several polycyclic
various resonance structures of nitrobenzene. aromatic compounds (containing more than
:O ⊕ two fused benzene rings) are produced by
:

:O ⊕ O
: :

N N O incomplete combustion of tobacco, coal and

⊕ petroleum. In liver, benzene is oxidized to an
epoxide. Benzopyrene is converted into an
epoxy diol. These substances are carcinogenic
Resonating structures
and can react with DNA which can induce
mutation leading to uncontrolled growth of
⊕ O :O ⊕
:

:O ⊕
: :

: :

:O O O cancer cells.
N N N
⊕

Internet my friend

1. chemed.chem.purdue.edu>1organic>Organic Chemistry
2. www.ncert.nic.in>ncerts>kech206(pdf)
3. https://www.britannica.com>science>benzene
4. https://pubchem.ncbi.nlm.nih.gov>Benzene

258
 Exercises

1. Choose correct options

A. Which of the following compound E. Arrange the three isomers of alkane
has highest boiling point ? with malecular formula C5H12 in
a. n-pentane increasing order of boiling points and
b. iso-butane write their IUPAC names.
c. butane F. Write IUPAC names of the products
d. neopentane obtained by the reaction of cold
B. Acidic hydrogen is present in : concentrated sulphuric acid followed by
a. acetylene water with the following compounds.
b. ethane a. propene b. but-l-ene
c. ethylene G. Write the balanced chemical reaction
d. dimethyl acetylene for preparation of ethane from
C. Identify 'A' in the following reaction: a. Ethyl bromide
A
CH3 - C = CH2 CH3- C - CH3 b. Ethyl magnesium iodide
CH3 O H. How many monochlorination products
are possible for
+ CO2 + H2O a. 2-methylpropane ?
a. KMnO4/H+ b. 2-methylbutane ?
b. alkaline KMnO4 Draw their structures and write their
c. dil. H2SO4/1% HgSO4 IUPAC names.
d. NaOH/H2O2 I. Write all the possible products for
D. Major product of chlorination of pyrolysis of butane.
ethyl benzene is : J. Which of the following will exhibit
a. m-chlorethyl benzene geometical isomerism ?
b. p - chloroethyl benzene a. CH3- CH2 - C - CH3
c. chlorobenzene CH2
d. o - chloroethylbenzene
E. 1 - chloropropane on treatment with b (CH3)2 C = CH2
alc. KOH produces :
a. propane c. CH3- C = C - CH3
b. propene C2H5 C2H5
c. propyne K. What is the action of following on
d. propyl alcohol ethyl iodide ?
2. Name the following : a. alc, KOH
A. The type of hydrocarbon that is used b. Zn, HCl
as lubricant. L. An alkene ‘A’ an ozonolysis gives 2
B. Alkene used in the manufacture of moles of ethanal. Write the structure
polythene bags. and IUPAC name of ‘A’.
C. The hydrocarbon said to possess M. Acetone and acetaldehyde are the
carcinogenic property. ozonolysis products of an alkene.
D. What are the main natural sources of Write the structural formula of an
alkane? alkene and give IUPAC name of it.
N. Write the reaction to convert
a. propene to nypropylalcohol.
b. propene to isoproyl alcohol.
259
 O. What is the action of following on 6. Identify giving reason whether the
but-2-ene ? following compounds are aromatic or
a. dil alkaline KMnO4 not.
b. acidic KMnO4 A.
P. Complete the following reaction
sequence :
HC ≡ CH
LiNH 2
A
CH CH Cl
B
3
HBr2
C B.
Comment on the acidic nature of B.
Q. Write the balanced chemical reactions C.
to get benzene from
a. Sodium benzoate.
b. Phenol. D.
R. Predict the possible products of the N
following reaction. 7. Name two reagents used for acylation
a. chlorination of nitrobenzene, of benzene.
b. sulfonation of chlorobenzene, 8. Read the following reaction and
c. bromination of phenol, answer the questions given below.
d. nitration of toluene.
3. Identify the main product of the
anhydrous
reaction + CH3Cl
AlCl3
O2
a. CH3-CH2-CH3
∆
60% H SO
b. CH3 - CH - CH3 2 4
CH3
373K
OH
+ HCl
H2
c. HC ≡ C-CH3 A. Write the name of the reaction.
Pd-C/quinoline
B. Identify the electrophile in it.
C. How is this electrophile generated?
40% H2SO4
d. H-C≡CH3+H2O
1% HgSO4
Activity :
4. Read the following reaction and
answer the questions given below. Prepare chart of hydrocarbons and
benzoyl
CH3 - C = CH2 + HBr peroxide note down the characteristics.
CH3

CH3 - CH- CH2Br

a. Write IUPAC name of the product.
b. State the rule that governs formation
of this product.
5. Identify A, B, C in the following
reaction sequence :
Br2/CCl4
CH3 - CH = CH2 room temperature
A
Zn dil. alka.
B KMnO4
C

260