Hydrocarbons 295

Unit 9

Hydrocarbons

Hydrocarbons are the important sources of energy.

After studying this unit, you will be

able to
• name hydrocarbons according to The term ‘hydrocarbon’ is self-explanatory which means
IUPAC system of nomenclature; compounds of carbon and hydrogen only. Hydrocarbons
• recognise and write structures play a key role in our daily life. You must be familiar
of isomers of alkanes,
with the terms ‘LPG’ and ‘CNG’ used as fuels. LPG is the
alkenes, alkynes and aromatic
abbreviated form of liquified petroleum gas whereas CNG
hydrocarbons;
• learn about various methods of
stands for compressed natural gas. Another term ‘LNG’
preparation of hydrocarbons; (liquified natural gas) is also in news these days. This is
• distinguish between alkanes, also a fuel and is obtained by liquifaction of natural gas.
alkenes, alkynes and aromatic Petrol, diesel and kerosene oil are obtained by the fractional
hydrocarbons on the basis of distillation of petroleum found under the earth’s crust.
physical and chemical properties; Coal gas is obtained by the destructive distillation of
• draw and differentiate between coal. Natural gas is found in upper strata during drilling
various conformations of ethane; of oil wells. The gas after compression is known as
• appreciate the role of compressed natural gas. LPG is used as a domestic fuel
hydrocarbons as sources of
with the least pollution. Kerosene oil is also used as a
energy and for other industrial
applications;
domestic fuel but it causes some pollution. Automobiles
• predict the formation of need fuels like petrol, diesel and CNG. Petrol and CNG
the addition products of operated automobiles cause less pollution. All these fuels
unsymmetrical alkenes and contain mixture of hydrocarbons, which are sources of
alkynes on the basis of electronic energy. Hydrocarbons are also used for the manufacture
mechanism; of polymers like polythene, polypropene, polystyrene etc.
• comprehend the structure of Higher hydrocarbons are used as solvents for paints. They
benzene, explain aromaticity are also used as the starting materials for manufacture
and understand mechanism of many dyes and drugs. Thus, you can well understand
of electrophilic substitution
the importance of hydrocarbons in your daily life. In this
reactions of benzene;
• predict the directive influence of
unit, you will learn more about hydrocarbons.
substituents in monosubstituted
9.1 CLASSIFICATION
benzene ring;
• learn about carcinogenicity and Hydrocarbons are of different types. Depending upon
toxicity. the types of carbon-carbon bonds present, they can
be classified into three main categories – (i) saturated

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(ii) unsaturated and (iii) aromatic of the general formula for alkane family
hydrocarbons. Saturated hydrocarbons or homologous series? If we examine the
contain carbon-carbon and carbon-hydrogen formula of different alkanes we find that
single bonds. If different carbon atoms are the general formula for alkanes is CnH2n+2. It
joined together to form open chain of carbon represents any particular homologue when n
atoms with single bonds, they are termed is given appropriate value. Can you recall the
as alkanes as you have already studied in structure of methane? According to VSEPR
Unit 8. On the other hand, if carbon atoms theory (Unit 4), methane has a tetrahedral
form a closed chain or a ring, they are termed structure (Fig. 9.1), in which carbon atom lies
as cycloalkanes. Unsaturated hydrocarbons at the centre and the four hydrogen atoms lie
contain carbon-carbon multiple bonds – at the four corners of a regular tetrahedron.
double bonds, triple bonds or both. Aromatic All H-C-H bond angles are of 109.5°.
hydrocarbons are a special type of cyclic
compounds. You can construct a large
number of models of such molecules of both
types (open chain and close chain) keeping
in mind that carbon is tetravalent and
hydrogen is monovalent. For making models
of alkanes, you can use toothpicks for bonds
and plasticine balls for atoms. For alkenes,
alkynes and aromatic hydrocarbons, spring
models can be constructed. Fig. 9.1 Structure of methane
In alkanes, tetrahedra are joined together
9.2 ALKANES
in which C-C and C-H bond lengths are
As already mentioned, alkanes are saturated
154 pm and 112 pm respectively (Unit 8).
open chain hydr ocarbons containing
You have already read that C–C and C–H σ
carbon - carbon single bonds. Methane (CH4)
bonds are formed by head-on overlapping of
is the first member of this family. Methane is 3
sp hybrid orbitals of carbon and 1s orbitals
a gas found in coal mines and marshy places.
of hydrogen atoms.
If you replace one hydrogen atom of methane
by carbon and join the required number of 9.2.1 Nomenclature and Isomerism
hydrogens to satisfy the tetravalence of the You have already read about nomenclature
other carbon atom, what do you get? You of different classes of organic compounds
get C2H6. This hydrocarbon with molecular in Unit 8. Nomenclature and isomerism
formula C2H6 is known as ethane. Thus you in alkanes can further be understood with
can consider C2H6 as derived from CH4 by the help of a few more examples. Common
replacing one hydrogen atom by -CH3 group. names are given in parenthesis. First three
Go on constructing alkanes by doing this alkanes – methane, ethane and propane have
theoretical exercise i.e., replacing hydrogen only one structure but higher alkanes can
atom by –CH3 group. The next molecules will have more than one structure. Let us write
be C3H8, C4H10 … structures for C4H10. Four carbon atoms of
H H H C4H10 can be joined either in a continuous
replace any H by - CH3 chain or with a branched chain in the
H—C—H H—C—C—H or C2H6
following two ways :
H H H I
These hydrocarbons are inert under
normal conditions as they do not react with
acids, bases and other reagents. Hence,
they were earlier known as paraffins (latin :
parum, little; affinis, affinity). Can you think Butane (n- butane), (b.p. 273 K)

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II isomers. It is also clear that structures I and

III have continuous chain of carbon atoms
but structures II, IV and V have a branched
chain. Such structural isomers which differ
in chain of carbon atoms are known as chain
isomers. Thus, you have seen that C4H10
2-Methylpropane (isobutane) and C5H12 have two and three chain isomers
(b.p.261 K) respectively.
In how many ways, you can join five Problem 9.1
carbon atoms and twelve hydrogen atoms of Write structures of different chain
C5H12? They can be arranged in three ways isomers of alkanes corresponding to the
as shown in structures III–V molecular formula C6H14. Also write their
III IUPAC names.

Solution
(i) CH3 – CH2 – CH2 – CH2– CH2– CH3
n-Hexane
Pentane (n-pentane)
(b.p. 309 K)

IV
2-Methylpentane

3-Methylpentane

2-Methylbutane (isopentane)
(b.p. 301 K)
2,3-Dimethylbutane
V

2,2 - Dimethylbutane

Based upon the number of carbon atoms

attached to a carbon atom, the carbon atom is
2,2-Dimethylpropane (neopentane) termed as primary (1°), secondary (2°), tertiary
(b.p. 282.5 K) (3°) or quaternary (4°). Carbon atom attached
Structures I and II possess same molecular to no other carbon atom as in methane or to
formula but differ in their boiling points and only one carbon atom as in ethane is called
other properties. Similarly structures III, IV primary carbon atom. Terminal carbon
and V possess the same molecular formula atoms are always primary. Carbon atom
but have different properties. Structures I and attached to two carbon atoms is known as
II are isomers of butane, whereas structures secondary. Tertiary carbon is attached to
III, IV and V are isomers of pentane. Since three carbon atoms and neo or quaternary
difference in properties is due to difference in carbon is attached to four carbon atoms. Can
their structures, they are known as structural you identify 1°, 2°, 3° and 4° carbon atoms in

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structures I to V ? If you go on constructing compounds. These groups or substituents

structures for higher alkanes, you will be are known as alkyl groups as they are derived
getting still larger number of isomers. C6H14 from alkanes by removal of one hydrogen
has got five isomers and C7H16 has nine. As atom. General formula for alkyl groups is
many as 75 isomers are possible for C10H22. CnH2n+1 (Unit 8).
In structures II, IV and V, you observed Let us recall the general rules for
that –CH3 group is attached to carbon atom nomenclature already discussed in Unit 8.
numbered as 2. You will come across groups Nomenclature of substituted alkanes can
like –CH 3, –C 2H 5, –C 3H 7 etc. attached to further be understood by considering the
carbon atoms in alkanes or other classes of following problem:

Problem 9.2
Write structures of different isomeric alkyl groups corresponding to the molecular formula
C5H11. Write IUPAC names of alcohols obtained by attachment of –OH groups at different
carbons of the chain.
Solution
Structures of – C5H11 group Corresponding alcohols Name of alcohol

(i) CH3 – CH2 – CH2 – CH2– CH2 – CH3 – CH2 – CH2 – CH2– CH2 – OH Pentan-1-ol

(ii) CH3 – CH – CH2 – CH2 – CH3 CH3 – CH – CH2 – CH2– CH3 Pentan-2-ol
| |
OH

(iii) CH3 – CH2 – CH – CH2 – CH3 CH3 – CH2 – CH – CH2– CH3 Pentan-3-ol
| |
OH

CH3 CH3 3-Methyl-

| | butan-1-ol
(iv) CH3 – CH – CH2 – CH2 – CH3 – CH – CH2 – CH2– OH

CH3 CH3 2-Methyl-

| | butan-1-ol
(v) CH3 – CH2 – CH – CH2 – CH3 – CH2 – CH – CH2– OH

CH3 CH3 2-Methyl-

| | butan-2-ol
(vi) CH3 – C – CH2 – CH3 CH3 – C – CH2 – CH3
| |
OH
CH3 CH3 2,2- Dimethyl-
| | propan-1-ol
(vii) CH3 – C – CH2 – CH3 – C – CH2OH
| |
CH3 CH3

CH3 CH3 OH 3-Methyl-

| | | | butan-2-ol
(viii) CH3 – CH – CH –CH3 CH3 – CH – CH –CH3

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Table 9.1 Nomenclature of a Few Organic Compounds

Structure and IUPAC Name Remarks

Lowest sum and

1 2 3 4 5 6
(a) CH3– CH – CH2 – CH – CH2 – CH3 alphabetical
(4 – Ethyl – 2 – methylhexane) arrangement

Lowest sum and

8 7 6 5 4 3 2 1
(b) CH3 – CH2 – CH2 – CH – CH – C – CH2 – CH3 alphabetical
arrangement

(3,3-Diethyl-5-isopropyl-4-methyloctane)

1 2 3 4 5 6 7 8 9 10 sec is not considered

(c) CH3– CH2– CH2– CH– CH– CH2– CH2– CH2– CH2– CH3 while arranging
alphabetically;
isopropyl is taken
5-sec– Butyl-4-isopropyldecane
as one word
1 2 3 4 5 6 7 8 9
(d) CH3– CH2– CH2– CH2– CH– CH2– CH2– CH2– CH3
Further numbering
to the substituents
of the side chain

5-(2,2– Dimethylpropyl)nonane
1 2 3 4 5 6 7
(e) CH3 – CH2 – CH – CH2 – CH – CH2 – CH3
Alphabetical
priority order
3–Ethyl–5–methylheptane

Problem 9.3 important to write the correct structure

from the given IUPAC name. To do this, first
Write IUPAC names of the following
of all, the longest chain of carbon atoms
compounds :
corresponding to the parent alkane is written.
(i) (CH3)3 C CH2C(CH3)3 Then after numbering it, the substituents are
(ii) (CH3)2 C(C2H5)2 attached to the correct carbon atoms and
(iii) tetra – tert-butylmethane finally valence of each carbon atom is satisfied
by putting the correct number of hydrogen
Solution atoms. This can be clarified by writing the
(i) 2, 2, 4, 4-Tetramethylpentane structure of 3-ethyl-2, 2–dimethylpentane in
(ii) 3, 3-Dimethylpentane the following steps :
(iii) 3,3-Di-tert-butyl -2, 2, 4, 4 - i) Draw the chain of five carbon atoms:
tetramethylpentane C–C–C–C–C
If it is important to write the correct ii) Give number to carbon atoms:
1 2 3 4 5
IUPAC name for a given structure, it is equally C –C –C –C –C

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iii) Attach ethyl group at carbon 3 and two Longest chain is of six carbon atoms and
methyl groups at carbon 2 not that of five. Hence, correct name is
3-Methylhexane.
7 6 5 4 3 2 1
1 2 3 4 5
C – C– C– C– C
(ii) CH3 – CH2 – CH – CH2 – CH – CH2 – CH3

iv) Satisfy the valence of each carbon atom

by putting requisite number of hydrogen Numbering is to be started from the
atoms : end which gives lower number to ethyl
group. Hence, correct name is 3-ethyl-5-
methylheptane.
CH3 – C – CH – CH2 – CH3
9.2.2 Preparation

Petroleum and natural gas are the main
Thus we arrive at the correct structure. sources of alkanes. However, alkanes can be
If you have understood writing of structure prepared by following methods :
from the given name, attempt the following
problems. 1. From unsaturated hydrocarbons
Dihydrogen gas adds to alkenes and alkynes
Problem 9.4 in the presence of finely divided catalysts like
Write structural formulas of the following platinum, palladium or nickel to form alkanes.
compounds : This process is called hydrogenation. These
(i) 3, 4, 4, 5–Tetramethylheptane metals adsorb dihydrogen gas on their
surfaces and activate the hydrogen – hydrogen
(ii) 2,5-Dimethyhexane bond. Platinum and palladium catalyse the
Solution reaction at room temperature but relatively
higher temperature and pressure are required
with nickel catalysts.
(i) CH3 – CH2 – CH – C – CH– CH – Pt/Pd/Ni
CH 2 =CH 2 + H 2 CH 3 −CH 3
CH3
EthenePropane (9.1)
Pt/Pd/Ni
CH 2–CH=CH 2 + H 2 CH 3−CH 2CH 3
PropanePropane
   
(ii) CH3 – CH – CH2 – CH2 – CH – CH3 (9.2)
Pt/Pd/Ni
Problem 9.5 CH 3–C≡ C–H + 2H CH 3−CH 2CH 3
Writ e stru ctu r es fo r each o f t h e PropynePropane
following compounds. Why are the given
(9.3)
names incorrect? Write correct IUPAC
names.
2. From alkyl halides
(i) 2-Ethylpentane
i) Alkyl halides (except fluorides) on reduction
(ii) 5-Ethyl – 3-methylheptane with zinc and dilute hydrochloric acid give
Solution alkanes.
(i) CH3 – CH – CH2– CH2 – CH3 +
Zn,H
CH–C1+H2 CH4+HC1 (9.4)

Chloromethane Methane

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Hydrocarbons 301

C2H5–C1+H2 Zn,H
+
C2H6+HC1 alkane containing even number of
Chloroethane Ethane (9.5) carbon atoms at the anode.
− +
2CH3COO Na + 2H2O
CH3CH2CH3+CH1
+
CH3CH2CH2C1 + H2 Zn,H

1-Chloropropane Propane Sodium acetate

(9.6) ↓ Electrolysts
ii) Alkyl halides on treatment with sodium CH3 − CH3 + 2CO2 + H2 + 2NaOH
(9.9)
metal in dry ethereal (free from moisture)
solution give higher alkanes. This reaction The reaction is supposed to follow the
is known as Wurtz reaction and is used following path :
O
for the preparation of higher alkanes
– + – +
containing even number of carbon i) 2CH3COO Na 2CH3 – C – O +2Na
atoms.
ii) At anode:
CH3Br+2Na+BrCH3 dry ether CH3+2Na
O O
Bromomenthane Ethane – –02e– .
(9.7) 2CH3 –C–O 2CH3 – C – 2CH3+2CO2↑
C2H5br+2Na+BrC2H5 dry ether C2H5–C2H Acetate ion Acetate Methyl free
free radical radical
Bromoethane n–Butane iii) H3C + CH3 H3C–CH3↑
(9.8) iv) At cathode :
What will happen if two different alkyl halides
are taken? H2O+e–→–OH+
2 →H2↑
3. From carboxylic acids
i) Sodium salts of carboxylic acids on Methane cannot be prepared by this
heating with soda lime (mixture of sodium method. Why?
hydroxide and calcium oxide) give alkanes
9.2.3 Properties
containing one carbon atom less than the
carboxylic acid. This process of elimination Physical properties
of carbon dioxide from a carboxylic acid is Alkanes are almost non-polar molecules
known as decarboxylation. because of the covalent nature of C-C and
– + CaO
C-H bonds and due to very little difference
CH3COO Na +MaOH ∆ CH4+NaCO3 of electronegativity between carbon and
Sodium ethanoate hydrogen atoms. They possess weak van der
Waals forces. Due to the weak forces, the first
Problem 9.6 four members, C1 to C4 are gases, C5 to C17
Sodium salt of which acid will be needed are liquids and those containing 18 carbon
for the preparation of propane ? Write atoms or more are solids at 298 K. They are
chemical equation for the reaction. colourless and odourless. What do you think
about solubility of alkanes in water based
Solution upon non-polar nature of alkanes? Petrol
Butanoic acid, is a mixture of hydrocarbons and is used
– +
CH3CH2CH2COO Na + NaOH CaO as a fuel for automobiles. Petrol and lower
fractions of petroleum are also used for dry
CH3CH2CH3+Na2CO3 cleaning of clothes to remove grease stains.
On the basis of this observation, what do
you think about the nature of the greasy
ii) Kolbe’s electrolytic method An aqueous substance? You are correct if you say that
solution of sodium or potassium salt of grease (mixture of higher alkanes) is non-
a carboxylic acid on electrolysis gives

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polar and, hence, hydrophobic in nature. It is reducing agents. However, they undergo
generally observed that in relation to solubility the following reactions under certain
of substances in solvents, polar substances conditions.
are soluble in polar solvents, whereas the
1. Substitution reactions
non-polar ones in non-polar solvents i.e., like
dissolves like. One or more hydrogen atoms of alkanes
can be replaced by halogens, nitro group
Boiling point (b.p.) of different alkanes are
and sulphonic acid group. Halogenation
given in Table 9.2 from which it is clear that
there is a steady increase in boiling point with takes place either at higher temperature
increase in molecular mass. This is due to the (573-773 K) or in the presence of diffused
fact that the intermolecular van der Waals sunlight or ultraviolet light. Lower alkanes
forces increase with increase of the molecular do not undergo nitration and sulphonation
size or the surface area of the molecule. reactions. These reactions in which hydrogen
atoms of alkanes are substituted are known
You can make an interesting observation
as substitution reactions. As an example,
by having a look on the boiling points of
three isomeric pentanes viz., (pentane, chlorination of methane is given below:
2-methylbutane and 2,2-dimethylpropane). It Halogenation
is observed (Table 9.2) that pentane having hv
a continuous chain of five carbon atoms has CH2 + C1 CH3C1 + HC1
the highest boiling point (309.1K) whereas Chloromethane (9.10)
2,2 – dimethylpropane boils at 282.5K. With
increase in number of branched chains, CH3C1 + hv
CH2 C12 + HC1
the molecule attains the shape of a sphere.
Dichloromethane (9.11)
This results in smaller area of contact and
therefore weak intermolecular forces between CH2C12 hv
CHC13 + HC1
spherical molecules, which are overcome at
Trichloromethane (9.12)
relatively lower temperatures.
hv
Chemical properties CHC13 + C12 CC14 + HC1
As already mentioned, alkanes are generally Tetrachloromethane (9.13)
inert towards acids, bases, oxidising and
Table 9.2 Variation of Melting Point and Boiling Point in Alkanes

Molecular Name Molecular b.p./(K) m.p./(K)

formula mass/u
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
C7H16 Heptane 100 371.4 182.4
C8H18 Octane 114 398.7 216.2
C9H20 Nonane 128 423.8 222.0
C10H22 Decane 142 447.1 243.3
C20H42 Eicosane 282 615.0 236.2

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hv steps are possible and may occur. Two such

CH3–CH3 + C12 CH3–CH2C1 + HC1
Chloroethane (9.14) steps given below explain how more highly
haloginated products are formed.
It is found that the rate of reaction of . .
alkanes with halogens is F2 > Cl2 > Br2 > I2. CH3C1 + C  1 → C  H2C1 + HC1
. .
Rate of replacement of hydrogens of alkanes is : C  H2C1 + C1– C1 → CH2C12 + C  1
3° > 2° > 1°. Fluorination is too violent to
be controlled. Iodination is very slow and a (iii) Termination: The reaction stops after
reversible reaction. It can be carried out in the some time due to consumption of reactants
presence of oxidizing agents like HIO3 or HNO3. and / or due to the following side reactions :
The possible chain terminating steps are:
CH4+I2 CH3I+HI(9.15) . .
(a) C  1 + C  1 → C1–C1
HIO3+5HI→312+3H2O(9.16) . .
(b) H3 C   + C   H3 → H3C– CH3
. .
Halogenation is supposed to proceed via (c) H3 C  1 + C  1 → H3C–C1
free radical chain mechanism involving three
Though in (c), CH3 – Cl, the one of the
steps namely initiation, propagation and
products is formed but free radicals are
termination as given below:
consumed and the chain is terminated. The
Mechanism above mechanism helps us to understand
(i) Initiation : The reaction is initiated the reason for the formation of ethane as a
by homolysis of chlorine molecule in the byproduct during chlorination of methane.
presence of light or heat. The Cl–Cl bond 2. Combustion
is weaker than the C–C and C–H bond and
Alkanes on heating in the presence of air or
hence, is easiest to break. dioxygen are completely oxidized to carbon
hv
. dioxide and water with the evolution of large
C1–C1 homolysis C H3 + C1 amount of heat.
Chlorine free radicals CH4 (g) + 202 (g) → CO2 (g) + 2H2O(1);
(ii) Propagation : Chlorine free radical Äc Hè − 890kJ mol-1
attacks the methane molecule and takes the (9.17)
reaction in the forward direction by breaking
C4H10 (g) + 13/2O2 (g) → 4CO2 (g) + 5H2O(1)
the C-H bond to generate methyl free radical
with the formation of H-Cl. Äc Hè = −2875.84kJ mol-1
+
(a) CH4 + C1 hv +
C H3 + H–C1 (9.18)
The general combustion equation for any
The methyl radical thus obtained attacks alkane is :
the second molecule of chlorine to form  3n + 1
CnH2n+2 +  O → nCO2 + (n + 1)H2O
CH3 – Cl with the liberation of another chlorine  2  2
free radical by homolysis of chlorine molecule. (9.19)
(b) CH3 + C1–C1 hv
CH3 – C1 + C1 Due to the evolution of large amount of
heat during combustion, alkanes are used as
The chlorine and methyl free radicals fuels.
generated above repeat steps (a) and (b) During incomplete combustion of alkanes
respectively and thereby setup a chain of with insufficient amount of air or dioxygen,
reactions. The propagation steps (a) and carbon black is formed which is used in
(b) are those which directly give principal the manufacture of ink, printer ink, black
products, but many other propagation pigments and as filters.

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CH4(g) + O2(g)
incomplete
C(s)+2H2 O(1) pressure in the presence of oxides of vanadium,
combustion
molybdenum or chromium supported over
(9.20)
alumina get dehydrogenated and cyclised to
3. Controlled oxidation benzene and its homologues. This reaction is
Alkanes on heating with a regulated supply known as aromatization or reforming.
of dioxygen or air at high pressure and in the
presence of suitable catalysts give a variety of
oxidation products.
3
(i) 2CH4 + O2 Cu/523K/100atm 2CH OH
Methanol
(9.21)
Mo2O3 (9.26)
(ii) CH4 + O2 HCHO + H2O
∆ Toluene (C 7H8) is methyl derivative of
Methanal
benzene. Which alkane do you suggest for
preparation of toluene ?
(9.22)
(CH3COO)Mn 6. Reaction with steam
(iii) 2CH3CH3 + 3O2 2CH3COOH
∆ Methane reacts with steam at 1273 K in the
Ethanoic acid presence of nickel catalyst to form carbon
+ 2H2O monoxide and dihydrogen. This method is
(9.23) used for industrial preparation of dihydrogen
(iv) Ordinarily alkanes resist oxidation but gas
alkanes having tertiary H atom can be Ni
oxidized to corresponding alcohols by CH4 + H2IO CO + 3H2(9.27)
∆
potassium permanganate.
KMnO4 7. Pyrolysis
(iCH3)3 CH Oxidation (CH3)3 COH Higher alkanes on heating to higher
2-Methylpropane2-Methylpropane-2-01 temperature decompose into lower alkanes,
alkenes etc. Such a decomposition reaction
(9.24) into smaller fragments by the application of
4. Isomerisation heat is called pyrolysis or cracking.
n-Alkanes on heating in the presence of
anhydrous aluminium chloride and hydrogen
chloride gas isomerise to branched chain
alkanes. Major products are given below.
Some minor products are also possible which
you can think over. Minor products are (9.28)
generally not reported in organic reactions. Pyrolysis of alkanes is believed to be a
free radical reaction. Preparation of oil gas
CH3(CH)2)4CH3 Anhy, AICI / HCI 3

or petrol gas from kerosene oil or petrol

n-Hexane involves the principle of pyrolysis. For
CH3CH–(CH2)2–CH3+CH3CH2–CH–CH2–CH3 example, dodecane, a constituent of kerosene
oil on heating to 973K in the presence of
CH3 CH3 platinum, palladium or nickel gives a mixture
2-Methylpen tane 3-Methylpenatone of heptane and pentene.
(9.25)

5. Aromatization C12H26 Pt/Pd/Ni

973K C7H16 + C5H10 Other
Products
n-Alkanes having six or more carbon atoms Dodecane Heptane Pentene
on heating to 773K at 10-20 atmospheric (9.29)

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Hydrocarbons 305

9.2.4 Conformations 1. Sawhorse projections

Alkanes contain carbon-carbon sigma (σ) In this projection, the molecule is viewed
bonds. Electron distribution of the sigma along the molecular axis. It is then projected
molecular orbital is symmetrical around the on paper by drawing the central C–C bond
internuclear axis of the C–C bond which is as a somewhat longer straight line. Upper
not disturbed due to rotation about its axis. end of the line is slightly tilted towards
This permits free rotation about C–C single right or left hand side. The front carbon is
bond. This rotation results into different shown at the lower end of the line, whereas
spatial arrangements of atoms in space the rear carbon is shown at the upper end.
which can change into one another. Such Each carbon has three lines attached to it
spatial arrangements of atoms which can corresponding to three hydrogen atoms.
be converted into one another by rotation The lines are inclined at an angle of 120° to
around a C-C single bond are called each other. Sawhorse projections of eclipsed
conformations or conformers or rotamers. and staggered conformations of ethane are
Alkanes can thus have infinite number of depicted in Fig. 9.2.
conformations by rotation around C-C single
bonds. However, it may be remembered that
rotation around a C-C single bond is not
completely free. It is hindered by a small
–1
energy barrier of 1-20 kJ mol due to weak
repulsive interaction between the adjacent
bonds. Such a type of repulsive interaction
is called torsional strain.
Conformations of ethane : Ethane Fig. 9.2 Sawhorse projections of ethane
molecule (C2H6) contains a carbon – carbon
single bond with each carbon atom attached 2. Newman projections
to three hydrogen atoms. Considering the In this projection, the molecule is viewed at the
ball and stick model of ethane, keep one C–C bond head on. The carbon atom nearer
carbon atom stationary and rotate the other to the eye is represented by a point. Three
carbon atom around the C-C axis. This hydrogen atoms attached to the front carbon
rotation results into infinite number of spatial atom are shown by three lines drawn at an
arrangements of hydrogen atoms attached to angle of 120° to each other. The rear carbon
one carbon atom with respect to the hydrogen atom (the carbon atom away from the eye) is
atoms attached to the other carbon atom. represented by a circle and the three hydrogen
These are called conformational isomers atoms are shown attached to it by the shorter
(conformers). Thus there are infinite number lines drawn at an angle of 120° to each other.
of conformations of ethane. However, there are The Newman’s projections are depicted in
two extreme cases. One such conformation Fig. 9.3.
in which hydrogen atoms attached to two
carbons are as closed together as possible is
called eclipsed conformation and the other in
which hydrogens are as far apart as possible
is known as the staggered conformation. Any
other intermediate conformation is called a
skew conformation.It may be remembered
that in all the conformations, the bond angles
and the bond lengths remain the same.
Eclipsed and the staggered conformations can
be represented by Sawhorse and Newman
projections.
Fig. 9.3 Newman’s projections of ethane

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306 chemistry

Relative stability of conformations: As the first member, ethylene or ethene (C2H4)

mentioned earlier, in staggered form of ethane, was found to form an oily liquid on reaction
the electron clouds of carbon-hydrogen bonds with chlorine.
are as far apart as possible. Thus, there are
9.3.1 Structure of Double Bond
minimum repulsive forces, minimum energy
and maximum stability of the molecule. On the Carbon-carbon double bond in alkenes
other hand, when the staggered form changes consists of one strong sigma (σ) bond (bond
–1
into the eclipsed form, the electron clouds of the enthalpy about 397 kJ mol ) due to head-on
2
carbon – hydrogen bonds come closer to each overlapping of sp hybridised orbitals and
other resulting in increase in electron cloud one weak pi (π) bond (bond enthalpy about
–1
repulsions. To check the increased repulsive 284 kJ mol ) obtained by lateral or sideways
forces, molecule will have to possess more overlapping of the two 2p orbitals of the two
energy and thus has lesser stability. As already carbon atoms. The double bond is shorter in
mentioned, the repulsive interaction between bond length (134 pm) than the C–C single
the electron clouds, which affects stability of bond (154 pm). You have already read that
a conformation, is called torsional strain. the pi (π) bond is a weaker bond due to poor
Magnitude of torsional strain depends upon sideways overlapping between the two 2p
the angle of rotation about C–C bond. This orbitals. Thus, the presence of the pi (π) bond
angle is also called dihedral angle or torsional makes alkenes behave as sources of loosely
angle. Of all the conformations of ethane, the held mobile electrons. Therefore, alkenes are
easily attacked by reagents or compounds
staggered form has the least torsional strain
which are in search of electrons. Such
and the eclipsed form, the maximum torsional
reagents are called electrophilic reagents.
strain. Therefore, staggered conformation is
The presence of weaker π-bond makes alkenes
more stable than the eclipsed conformation.
unstable molecules in comparison to alkanes
Hence, molecule largely remains in staggered
and thus, alkenes can be changed into single
conformation or we can say that it is preferred
bond compounds by combining with the
conformation. Thus it may be inferred that
electrophilic reagents. Strength of the double
rotation around C–C bond in ethane is not –1
bond (bond enthalpy, 681 kJ mol ) is greater
completely free. The energy difference between
than that of a carbon-carbon single bond in
the two extreme forms is of the order of 12.5 –1
–1 ethane (bond enthalpy, 348 kJ mol ). Orbital
kJ mol , which is very small. Even at ordinary
diagrams of ethene molecule are shown in
temperatures, the ethane molecule gains
Figs. 9.4 and 9.5.
thermal or kinetic energy sufficient enough to
–1
overcome this energy barrier of 12.5 kJ mol
through intermolecular collisions. Thus, it
can be said that rotation about carbon-carbon
single bond in ethane is almost free for all
practical purposes. It has not been possible to
separate and isolate different conformational
isomers of ethane.

9.3 Alkenes
Alkenes are unsaturated hydrocarbons
Fig. 9.4 Orbital picture of ethene depicting
containing at least one double bond. What
σ bonds only
should be the general formula of alkenes? If
there is one double bond between two carbon 9.3.2 Nomenclature
atoms in alkenes, they must possess two For nomenclature of alkenes in IUPAC system,
hydrogen atoms less than alkanes. Hence, the longest chain of carbon atoms containing
general formula for alkenes is CnH2n. Alkenes the double bond is selected. Numbering of the
are also known as olefins (oil forming) since chain is done from the end which is nearer to

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Unit 9.indd 306 11/10/2022 15:26:35

Hydrocarbons 307

Fig. 9.5 Orbital picture of ethene showing formation of (a) π-bond, (b) π-cloud and (c) bond angles and
bond lengths

the double bond. The suffix ‘ene’ replaces ‘ane’

of alkanes. It may be remembered that first Solution
member of alkene series is: CH2 (replacing (i) 2,8-Dimethyl-3, 6-decadiene;
n by 1 in CnH2n) known as methene but has (ii) 1,3,5,7 Octatetraene;
a very short life. As already mentioned, first
(iii) 2-n-Propylpent-1-ene;
stable member of alkene series is C2H4 known
as ethylene (common) or ethene (IUPAC). (iv) 4-Ethyl-2,6-dimethyl-dec-4-ene;
IUPAC names of a few members of alkenes
Problem 9.8
are given below :
Calculate number of sigma (σ) and pi (π)
Structure IUPAC name
bonds in the above structures (i-iv).
CH3 – CH = CH2 Propene
CH3 – CH2 – CH = CH2 But – l - ene Solution
CH3 – CH = CH–CH3 But-2-ene σ bonds : 33, π bonds : 2
CH2 = CH – CH = CH2 Buta – 1,3 - diene σ bonds : 17, π bonds : 4
CH2 = C – CH3 2-Methylprop-1-ene σ bonds : 23, π bond : 1
| σ bonds : 41, π bond : 1
CH3
CH2 = CH – CH – CH3 3-Methylbut-1-ene 9.3.3 Isomerism
|
CH3 Alkenes show both structural isomerism and
geometrical isomerism.
Structural isomerism : As in alkanes, ethene
Problem 9.7
(C2H4) and propene (C3H6) can have only one
Write IUPAC names of the following
structure but alkenes higher than propene
compounds:
have different structures. Alkenes possessing
(i) (CH3)2CH – CH = CH – CH2 – CH C4H8 as molecular formula can be written in

the following three ways:
CH3 – CH – CH
| I. 1 2 3 4
C2H5 CH2 = CH – CH2 – CH3

(ii) But-1-ene
(C4H8)
(iii) CH2 = C (CH2CH2CH3)2
(iv) CH3 CH2 CH2 CH2 CH2CH3 II. 1 2 3 4
| | CH3 – CH = CH – CH3
CH3 – CHCH = C – CH2 – CHCH3
| But-2-ene
CH3 (C4H8)

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308 chemistry

III. 1 2 3 In (a), the two identical atoms i.e., both

CH2 = C – CH3 the X or both the Y lie on the same side
| of the double bond but in (b) the two X or
CH3 two Y lie across the double bond or on the
2-Methyprop-1-ene opposite sides of the double bond. This
(C4H8) results in different geometry of (a) and (b) i.e.
disposition of atoms or groups in space in
Structures I and III, and II and III are
the two arrangements is different. Therefore,
the examples of chain isomerism whereas
they are stereoisomers. They would have the
structures I and II are position isomers.
same geometry if atoms or groups around
Problem 9.9 C=C bond can be rotated but rotation around
C=C bond is not free. It is restricted. For
Write structures and IUPAC names of
understanding this concept, take two pieces
different structural isomers of alkenes
of strong cardboards and join them with the
corresponding to C5H10.
help of two nails. Hold one cardboard in your
Solution one hand and try to rotate the other. Can
(a) CH2 = CH – CH2 – CH2 – CH3 you really rotate the other cardboard ? The
answer is no. The rotation is restricted. This
Pent-1-ene
illustrates that the restricted rotation of atoms
(b) CH3 – CH=CH – CH2 – CH3 or groups around the doubly bonded carbon
Pent-2-ene atoms gives rise to different geometries of
(c) CH3 – C = CH – CH3 such compounds. The stereoisomers of this
| type are called geometrical isomers. The
CH3 isomer of the type (a), in which two identical
2-Methylbut-2-ene atoms or groups lie on the same side of the
double bond is called cis isomer and the
(d) CH3 – CH – CH = CH2 other isomer of the type (b), in which identical
| atoms or groups lie on the opposite sides of
CH3 the double bond is called trans isomer . Thus
3-Methylbut-1-ene cis and trans isomers have the same structure
(e) CH2 = C – CH2 – CH3 but have different configuration (arrangement
| of atoms or groups in space). Due to different
CH3 arrangement of atoms or groups in space,
these isomers differ in their properties like
2-Methylbut-1-ene melting point, boiling point, dipole moment,
Geometrical isomerism: Doubly bonded solubility etc. Geometrical or cis-trans isomers
carbon atoms have to satisfy the remaining of but-2-ene are represented below :
two valences by joining with two atoms or
groups. If the two atoms or groups attached
to each carbon atom are different, they can
be represented by YX C = C XY like structure.
YX C = C XY can be represented in space in
the following two ways :

Cis form of alkene is found to be more

polar than the trans form. For example,
dipole moment of cis-but-2-ene is 0.33 Debye,
whereas, dipole moment of the trans form
is almost zero or it can be said that

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Unit 9.indd 308 10/10/2022 10:37:55 AM

Hydrocarbons 309

trans-but-2-ene is non-polar. This can be (ii) CH2 = CBr2

understood by drawing geometries of the two
forms as given below from which it is clear (iii) C6H5CH = CH – CH3
that in the trans-but-2-ene, the two methyl (iv) CH3CH = CCl CH3
groups are in opposite directions, Threfore,
dipole moments of C-CH3 bonds cancel, thus Solution
making the trans form non-polar. (iii) and (iv). In structures (i) and (ii), two
identical groups are attached to one of
the doubly bonded carbon atom.

9.3.4 Preparation
1. From alkynes: Alkynes on partial
reduction with calculated amount of
cis-But-2-ene trans-But-2-ene dihydrogen in the presence of palladised
(µ = 0.33D) (µ = 0) charcoal partially deactivated with poisons
In the case of solids, it is observed that the like sulphur compounds or quinoline give
trans isomer has higher melting point than alkenes. Partially deactivated palladised
the cis form. charcoal is known as Lindlar’s catalyst.
Alkenes thus obtained are having cis
Geometrical or cis-trans isomerism
geometry. However, alkynes on reduction
is also shown by alkenes of the types
XYC = CXZ and XYC = CZW with sodium in liquid ammonia form trans
alkenes.
Problem 9.10
Draw cis and trans isomers of the
following compounds. Also write their
IUPAC names :
(i) CHCl = CHCl (9.30)
(ii) C2H5CCH3 = CCH3C2H5

Solution

(9.31)
Pd/C
iii) CH≡ CH+H2 CH2 =CH2 (9.32)
Ethyne Ethene
Pd/C
CH3–C≡ CH+H2 CH3–CH =CH2
iv)
Propyne Propene
(9.33)
Wi l l p r o p e n e t h u s o b t a i n e d s h o w
Problem 9.11 geometrical isomerism? Think for the
Which of the following compounds will reason in support of your answer.
show cis-trans isomerism? 2. From alkyl halides: Alkyl halides (R-X) on
(i) (CH3)2C = CH – C2H5 heating with alcoholic potash (potassium
hydroxide dissolved in alcohol, say,

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Unit 9.indd 309 10/10/2022 10:37:55 AM

310 chemistry

ethanol) eliminate one molecule of halogen takes out one hydrogen atom from the
acid to form alkenes. This reaction is β-carbon atom.
known as dehydrohalogenation i.e.,
removal of halogen acid. This is example
of β-elimination reaction, since hydrogen
atom is eliminated from the β carbon atom
(carbon atom next to the carbon to which
halogen is attached).
(9.37)
9.3.5 Properties
Physical properties
Alkenes as a class resemble alkanes in
physical properties, except in types of
isomerism and difference in polar nature.
(9.34) The first three members are gases, the next
Nature of halogen atom and the alkyl fourteen are liquids and the higher ones are
group determine rate of the reaction. It solids. Ethene is a colourless gas with a faint
is observed that for halogens, the rate is: sweet smell. All other alkenes are colourless
iodine > bromine > chlorine, while for alkyl and odourless, insoluble in water but fairly
groups it is : tert > secondary > primary. soluble in non-polar solvents like benzene,
petroleum ether. They show a regular increase
3. From vicinal dihalides: Dihalides in
in boiling point with increase in size i.e., every
which two halogen atoms are attached
– CH2 group added increases boiling point by
to two adjacent carbon atoms are known
20–30 K. Like alkanes, straight chain alkenes
as vicinal dihalides. Vicinal dihalides on
have higher boiling point than isomeric
treatment with zinc metal lose a molecule
branched chain compounds.
of ZnX2 to form an alkene. This reaction
is known as dehalogenation. Chemical properties
Alkenes are the rich source of loosely held
CH2Br–CH2Br + Zn CH2=CH2+ ZnBr2 pi (π) electrons, due to which they show
(9.35) addition reactions in which the electrophiles
CH3CHBr–CH2Br + Zn CH3CH=CH2 add on to the carbon-carbon double bond to
form the addition products. Some reagents
+ZnBr2 also add by free radical mechanism. There
(9.36) are cases when under special conditions,
4. From alcohols by acidic dehydration: alkenes also undergo free radical substitution
You have read during nomenclature of reactions. Oxidation and ozonolysis reactions
different homologous series in Unit 12 are also quite prominent in alkenes. A brief
that alcohols are the hydroxy derivatives description of different reactions of alkenes
of alkanes. They are represented by R–OH is given below:
where, R is CnH2n+1. Alcohols on heating 1. Addition of dihydrogen: Alkenes add
with concentrated sulphuric acid form up one molecule of dihydrogen gas in
alkenes with the elimination of one water the presence of finely divided nickel,
molecule. Since a water molecule is palladium or platinum to form alkanes
eliminated from the alcohol molecule in (Section 9.2.2)
the presence of an acid, this reaction is 2. Addition of halogens : Halogens like
known as acidic dehydration of alcohols. bromine or chlorine add up to alkene to
This reaction is also the example of form vicinal dihalides. However, iodine
β-elimination reaction since –OH group does not show addition reaction under

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Unit 9.indd 310 11/10/2022 15:27:11

Hydrocarbons 311

normal conditions. The reddish orange

colour of bromine solution in carbon
tetrachloride is discharged when bromine
adds up to an unsaturation site. This
reaction is used as a test for unsaturation.
Addition of halogens to alkenes is an
example of electrophilic addition reaction
involving cyclic halonium ion formation (9.42)
which you will study in higher classes. Markovnikov, a Russian chemist made a
generalisation in 1869 after studying such
reactions in detail. These generalisations
led Markovnikov to frame a rule called
Markovnikov rule. The rule states that
negative part of the addendum (adding
(9.38) molecule) gets attached to that carbon atom
which possesses lesser number of hydrogen
atoms. Thus according to this rule, product
I i.e., 2-bromopropane is expected. In actual
practice, this is the principal product of the
reaction. This generalisation of Markovnikov
(9.39) rule can be better understood in terms of
mechanism of the reaction.
3. Addition of hydrogen halides: Hydrogen
halides (HCl, HBr,HI) add up to alkenes Mechanism
to for m alkyl halides. The order of Hydrogen bromide provides an electrophile,
+
reactivity of the hydrogen halides is H , which attacks the double bond to form
HI > HBr > HCl. Like addition of halogens carbocation as shown below :
to alkenes, addition of hydrogen halides is
also an example of electrophilic addition
reaction. Let us illustrate this by taking
addition of HBr to symmetrical and
unsymmetrical alkenes
Addition reaction of HBr to symmetrical
alkenes
(a) less stable (b) more stable
Addition reactions of HBr to symmetrical
primary carbocation secondary carbocation
alkenes (similar groups attached to double
bond) take place by electrophilic addition (i) The secondary carbocation (b) is more
mechanism. stable than the primary carbocation
(a), therefore, the former predominates
CH2=CH2+H–Br CH3–CH2–Br (9.40)
because it is formed at a faster rate.
–
CH3–CH=CH–CH3+HBr CH3–CH–CHCH3 (ii) The carbocation (b) is attacked by Br ion
to form the product as follows :
Br
(9.41)

Addition reaction of HBr to unsymmetrical

alkenes (Markovnikov Rule)
How will H – Br add to propene ? The two 2-Bromopropane
possible products are I and II. (major product)

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Unit 9.indd 311 10/27/2022 2:19:43 PM

312 chemistry

Anti Markovnikov addition or peroxide

effect or Kharash effect
In the presence of peroxide, addition of HBr
to unsymmetrical alkenes like propene takes
place contrary to the Markovnikov rule. This
happens only with HBr but not with HCl
The secondary free radical obtained in the
and Hl. This addition reaction was observed
above mechanism (step iii) is more stable than
by M.S. Kharash and F.R. Mayo in 1933 the primary. This explains the formation of
at the University of Chicago. This reaction 1-bromopropane as the major product. It may
is known as peroxide or Kharash effect be noted that the peroxide effect is not observed
or addition reaction anti to Markovnikov in addition of HCl and HI. This may be due
rule. to the fact that the H–Cl bond being
–1
(C6H5CO)2O2 stronger (430.5 kJ mol ) than H–Br bond
CH3 – CH=CH2+HBr CH3–CH2 –1
(363.7 kJ mol ), is not cleaved by the free
radical, whereas the H–I bond is weaker
CH2Br –1
(296.8 kJ mol ) and iodine free radicals
1–Bromopropane combine to form iodine molecules instead of
adding to the double bond.
(9.43)

Mechanism : Peroxide effect proceeds via Problem 9.12

free radical chain mechanism as given below: Write IUPAC names of the products
obtained by addition reactions of HBr to
(i)
hex-1-ene
(i) in the absence of peroxide and
(ii) in the presence of peroxide.

Solution

. Homolysis .
(ii) C 6H5+H–Br C6H3+ B r

4. Addition of sulphuric acid : Cold

concentrated sulphuric acid adds to
alkenes in accordance with Markovnikov
rule to form alkyl hydrogen sulphate by
the electrophilic addition reaction.

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Unit 9.indd 312 10/10/2022 10:37:56 AM

Hydrocarbons 313

ketones and/or acids depending upon the

nature of the alkene and the experimental
conditions

(9.49)
+
KMnO4/H
CH3 – CH=CH–CH3 2CH3COOH
(9.44) But-2-ene Ethanoic acid
(9.50)
7. Ozonolysis : Ozonolysis of alkenes
involves the addition of ozone molecule to
alkene to form ozonide, and then cleavage
of the ozonide by Zn-H 2O to smaller
molecules. This reaction is highly useful
in detecting the position of the double
(9.45) bond in alkenes or other unsaturated
5. Addition of water : In the presence of a compounds.
few drops of concentrated sulphuric acid
alkenes react with water to form alcohols,
in accordance with the Markovnikov rule.

(9.51)
(9.46)
6. Oxidation: Alkenes on reaction with cold,
dilute, aqueous solution of potassium
permanganate (Baeyer’s reagent) produce
vicinal glycols. Decolorisation of KMnO4
solution is used as a test for unsaturation.

(9.52)
(9.47) 8. Polymerisation: You are familiar with
polythene bags and polythene sheets.
Polythene is obtained by the combination
of large number of ethene molecules at
high temperature, high pressure and
in the presence of a catalyst. The large
molecules thus obtained are called
(9.48) polymers. This reaction is known as
b) Acidic potassium permanganate or acidic polymerisation. The simple compounds
potassium dichromate oxidises alkenes to from which polymers are made are called

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Unit 9.indd 313 10/10/2022 10:37:57 AM

314 chemistry

monomers. Other alkenes also undergo are named as derivatives of the corresponding
polymerisation. alkanes replacing ‘ane’ by the suffix ‘yne’.
High temp./pressure
n(CH2 =CH2) Catalyst
—( CH2–CH2 —
) The position of the triple bond is indicated
Polythene by the first triply bonded carbon. Common
and IUPAC names of a few members of alkyne
(9.53) series are given in Table 9.2.
n(CH3 –CH=CH2)
High temp./pressure
—(CH–CH2 —
)n You have already learnt that ethyne and
Catalyst
propyne have got only one structure but
there are two possible structures for butyne –
CH3
(i) but-1-yne and (ii) but-2-yne. Since these
Polypropene two compounds differ in their structures
(9.54) due to the position of the triple bond, they
Polymers are used for the manufacture of plastic are known as position isomers. In how
bags, squeeze bottles, refrigerator dishes, toys, many ways, you can construct the structure
pipes, radio and T.V. cabinets etc. Polypropene for the next homologue i.e., the next alkyne
is used for the manufacture of milk crates, with molecular formula C5H8? Let us try to
plastic buckets and other moulded articles. arrange five carbon atoms with a continuous
Though these materials have now become chain and with a side chain. Following are the
common, excessive use of polythene and possible structures :
polypropylene is a matter of great concern for Structure IUPAC name
all of us. 1 2 3 4 5
I. HC≡ C– CH2– CH2– CH3 Pent–1-yne
9.4 Alkynes 1 2 3 4 5
Like alkenes, alkynes are also unsaturated II. H3C–C≡ C– CH2– CH3 Pent–2-yne
hydrocarbons. They contain at least one triple 4 3 2 1
bond between two carbon atoms. The number III. H3C–CH–C≡ CH 3-Methyl but–1-yne
|
of hydrogen atoms is still less in alkynes as
CH3
compared to alkenes or alkanes. Their general Structures I and II are position isomers
formula is CnH2n–2. and structures I and III or II and III are chain
The first stable member of alkyne series isomers.
is ethyne which is popularly known as
acetylene. Acetylene is used for arc welding Problem 9.13
purposes in the form of oxyacetylene flame Write structures of different isomers
th
obtained by mixing acetylene with oxygen corresponding to the 5 member of
gas. Alkynes are starting materials for a large alkyne series. Also write IUPAC names of
number of organic compounds. Hence, it all the isomers. What type of isomerism
is interesting to study this class of organic is exhibited by different pairs of isomers?
compounds.
Solution
9.4.1 Nomenclature and Isomerism th
5 member of alkyne has the molecular
In common system, alkynes are named as formula C6H10. The possible isomers are:
derivatives of acetylene. In IUPAC system, they
Table 9.2 Common and IUPAC Names of Alkynes (CnH2n–2)

Value of n Formula Structure Common name IUPAC name

2 C2H2 H-C≡CH Acetylene Ethyne
3 C3H4 CH3-C≡CH Methylacetylene Propyne
4 C4H6 CH3CH2-C≡CH Ethylacetylene But-1-yne
4 C4H6 CH3-C≡C-CH3 Dimethylacetylene But-2-yne

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Unit 9.indd 314 10/27/2022 2:18:58 PM

Hydrocarbons 315

(a) HC ≡ C – CH2 – CH2 – CH2 – CH3

Hex-1-yne
(b) CH3 – C ≡ C – CH2 – CH2 – CH3
Hex-2-yne
(c) CH3 – CH2 – C ≡ C – CH2– CH3
Hex-3-yne

3-Methylpent-1-yne

4-Methylpent-1-yne

4-Methylpent-2-yne
Fig. 9.6 Orbital picture of ethyne showing
(a) sigma overlaps (b) pi overlaps.

orbitals of the other carbon atom, which

undergo lateral or sideways overlapping to
3,3-Dimethylbut-1-yne form two pi (π) bonds between two carbon
atoms. Thus ethyne molecule consists of one
Position and chain isomerism shown by
C–C σ bond, two C–H σ bonds and two C–C
different pairs.
π bonds. The strength of C≡C bond (bond
-1
enthalpy 823 kJ mol ) is more than those
–1
9.4.2 Structure of Triple Bond of C=C bond (bond enthalpy 681 kJ mol )
–1
Ethyne is the simplest molecule of alkyne and C–C bond (bond enthalpy 348 kJ mol ).
series. Structure of ethyne is shown in The C≡C bond length is shorter (120 pm)
Fig. 9.6. than those of C=C (133 pm) and C–C (154
pm). Electron cloud between two carbon
Each carbon atom of ethyne has two sp
atoms is cylindrically symmetrical about the
hybridised orbitals. Carbon-carbon sigma (σ)
internuclear axis. Thus, ethyne is a linear
bond is obtained by the head-on overlapping
molecule.
of the two sp hybridised orbitals of the two
carbon atoms. The remaining sp hybridised 9.4.3 Preparation
orbital of each carbon atom undergoes
1. From calcium carbide: On industrial
overlapping along the internuclear axis with
scale, ethyne is prepared by treating
the 1s orbital of each of the two hydrogen
calcium carbide with water. Calcium
atoms for ming two C-H sigma bonds.
carbide is prepared by heating quick lime
H-C-C bond angle is of 180°. Each carbon
with coke. Quick lime can be obtained by
has two unhybridised p orbitals which are
heating limestone as shown in the following
perpendicular to each other as well as to the
reactions:
plane of the C-C sigma bond. The 2p orbitals
of one carbon atom are parallel to the 2p CaCO3 ∆ CaO + O2 (9.55)

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316 chemistry

CaO + 3C CaC2 + CO (9.56) the sp hybridised carbon atoms whereas

2
Calcium they are attached to sp hybridised carbon
3
carbide atoms in ethene and sp hybridised carbons
in ethane. Due to the maximum percentage of
CaC2 + 2H2O Ca(OH)2 + C2H2 (9.57) s character (50%), the sp hybridised orbitals
of carbon atoms in ethyne molecules have
2. From vicinal dihalides : Vicinal dihalides
highest electronegativity; hence, these attract
on treatment with alcoholic potassium
the shared electron pair of the C-H bond of
hydroxide undergo dehydrohalogenation.
ethyne to a greater extent than that of the
One molecule of hydrogen halide is 2
sp hybridised orbitals of carbon in ethene
eliminated to form alkenyl halide which 3
and the sp hybridised orbital of carbon in
on treatment with sodamide gives alkyne.
ethane. Thus in ethyne, hydrogen atoms
can be liberated as protons more easily as
compared to ethene and ethane. Hence,
hydrogen atoms of ethyne attached to triply
bonded carbon atom are acidic in nature. You
may note that the hydrogen atoms attached
to the triply bonded carbons are acidic but
not all the hydrogen atoms of alkynes.
– +
HC ≡ CH + Na → HC ≡ C Na + 1/2 H2
9.4.4 Properties
Monosodium
Physical properties ethynide
Physical properties of alkynes follow the same
(9.59)
trend of alkenes and alkanes. First three – + – + – +
members are gases, the next eight are liquids HC ≡ C Na + Na → Na C Na ≡ C Na + 1/2 H2
and the higher ones are solids. All alkynes Disodium ethynide
are colourless. Ethyene has characteristic
(9.60)
odour. Other members are odourless. Alkynes + –
are weakly polar in nature. They are lighter CH3 – C ≡ C – H + Na NH 2
than water and immiscible with water but ↓
– +
soluble in organic solvents like ethers, carbon CH3 – C ≡ C Na + NH3
tetrachloride and benzene. Their melting Sodium propynide (9.61)
point, boiling point and density increase with
These reactions are not shown by alkenes
increase in molar mass.
and alkanes, hence used for distinction
Chemical properties between alkynes, alkenes and alkanes. What
Alkynes show acidic nature, addition reactions about the above reactions with but-1-yne and
and polymerisation reactions as follows : but-2-yne ? Alkanes, alkenes and alkynes
A. Acidic character of alkyne: Sodium follow the following trend in their acidic
metal and sodamide (NaNH 2) are strong behaviour :
bases. They react with ethyne to form sodium
acetylide with the liberation of dihydrogen i) CH ≡ CH > H2C – CH2 > CH3 –CH3
gas. These reactions have not been observed ii) HC ≡ CH > CH3 –C≡ CH >> CH3 –C≡C–CH3
in case of ethene and ethane thus indicating
that ethyne is acidic in nature in comparison B. Addition reactions: Alkynes contain a
to ethene and ethane. Why is it so ? Has triple bond, so they add up, two molecules of
it something to do with their structures dihydrogen, halogen, hydrogen halides etc.
and the hybridisation ? You have read that Formation of the addition product takes place
hydrogen atoms in ethyne are attached to according to the following steps.

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Hydrocarbons 317

The addition product formed depends

upon stability of vinylic cation. Addition in
unsymmetrical alkynes takes place according
to Markovnikov rule. Majority of the reactions
of alkynes are the examples of electrophilic
addition reactions. A few addition reactions
are given below: (9.66)
(i) Addition of dihydrogen (iv) Addition of water
HC≡CH+H2 Pt/Pd/Ni
[H2C = CH2] H2
CH3–CH3 Like alkanes and alkenes, alkynes are also
immiscible and do not react with water.
(9.62) However, one molecule of water adds to
Pt/Pd/Ni
alkynes on warming with mercuric sulphate
CH3–C≡CH + H2 [CH3–CH=CH2] and dilute sulphuric acid at 333 K to form
Propyne Propene carbonyl compounds.
↓H2
CH3–CH2–CH3
Propane
(9.63)
(ii) Addition of halogens

(9.67)

(9.64)
Reddish orange colour of the solution
of bromine in carbon tetrachloride is
decolourised. This is used as a test for
unsaturation.
(iii) Addition of hydrogen halides (9.68)
Two molecules of hydrogen halides (HCl, HBr, (v) Polymerisation
HI) add to alkynes to form gem dihalides (in (a) Linear polymerisation: Under suitable
which two halogens are attached to the same conditions, linear polymerisation of ethyne
carbon atom) takes place to produce polyacetylene or
H–C≡C–H+H–Br [CH2 = CH–Br]→ CHBr2 polyethyne which is a high molecular
Bromoethene weight polyene containing repeating units of
CH3 (CH = CH – CH = CH ) and can be represented
1,1-Dibromoethane as —( CH = CH – CH = CH )n— Under special
(9.65) conditions, this polymer conducts electricity.

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318 chemistry

Thin film of polyacetylene can be used as but in a majority of reactions of aromatic

electrodes in batteries. These films are good compounds, the unsaturation of benzene ring
conductors, lighter and cheaper than the is retained. However, there are examples of
metal conductors. aromatic hydrocarbons which do not contain a
(b) Cyclic polymerisation: Ethyne on benzene ring but instead contain other highly
passing through red hot iron tube at 873K unsaturated ring. Aromatic compounds
undergoes cyclic polymerization. Three containing benzene ring are known as
molecules polymerise to form benzene, which benzenoids and those not containing a
is the starting molecule for the preparation of benzene ring are known as non-benzenoids.
derivatives of benzene, dyes, drugs and large Some examples of arenes are given
number of other organic compounds. This is below:
the best route for entering from aliphatic to
aromatic compounds as discussed below:

Benzene Toluene Naphthalene

(9.69)

Problem 9.14 Biphenyl

How will you convert ethanoic acid into
benzene? 9.5.1 Nomenclature and Isomerism
The nomenclature and isomerism of aromatic
Solution hydrocarbons has already been discussed in
Unit 8. All six hydrogen atoms in benzene
are equivalent; so it forms one and only one
type of monosubstituted product. When two
hydrogen atoms in benzene are replaced by
two similar or different monovalent atoms or
groups, three different position isomers are
possible. The 1, 2 or 1, 6 is known as the ortho
(o–), the 1, 3 or 1, 5 as meta (m–) and the 1,
4 as para (p–) disubstituted compounds. A
few examples of derivatives of benzene are
given below:

9.5 Aromatic Hydrocarbon

These hydrocarbons are also known as
‘arenes’. Since most of them possess pleasant
odour (Greek; aroma meaning pleasant
smelling), the class of compounds was Methylbenzene 1,2-Dimethylbenzene
named as ‘aromatic compounds’. Most of such
compounds were found to contain benzene (Toluene) (o-Xylene)
ring. Benzene ring is highly unsaturated

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Unit 9.indd 318 11/10/2022 15:28:31

Hydrocarbons 319

Friedrich August Kekulé,a German chemist was born in 1829 at Darmsdt in

Germany. He became Professor in 1856 and Fellow of Royal Society in 1875. He
made major contribution to structural organic chemistry by proposing in 1858 that
carbon atoms can join to one another to form chains and later in 1865,he found
an answer to the challenging problem of benzene structure by suggesting that
these chains can close to form rings. He gave the dynamic structural formula to
benzene which forms the basis for its modern electronic structure. He described
the discovery of benzene structure later as:
FRIEDRICH
“I was sitting writing at my textbook,but the work did not progress; my thoughts
AUGUST KEKULÉ
were elsewhere. I turned my chair to the fire, and dozed. Again the atoms were
(7th September
gambolling before my eyes. This time the smaller groups kept modestly in the
1829–13th July
background. My mental eye, rendered more acute by repeated visions of this
1896)
kind, could now distinguish larger structures of manifold conformations; long
rows,sometimes more closely fitted together; all twisting and turning in snake like motion. But look! What
was that? One of the snakes had seized hold of it’s own tail, and the form whirled mockingly before my
eyes. As if by a flash of lightning I woke;.... I spent the rest of the night working out the consequences of
the hypothesis. Let us learn to dream, gentlemen, and then perhaps we shall learn the truth but let us
beware of making our dreams public before they have been approved by the waking mind.”( 1890).
One hundred years later, on the occasion of Kekulé’s centenary celebrations a group of compounds
having polybenzenoid structures have been named as Kekulenes.

was further found to produce one and only one

monosubstituted derivative which indicated
that all the six carbon and six hydrogen atoms
of benzene are identical. On the basis of this
observation August Kekulé in 1865 proposed
the following structure for benzene having
cyclic arrangement of six carbon atoms with
1,3 Dimethylbenzene 1,4-Dimethylbenzene alternate single and double bonds and one
(m-Xylene) ( p-Xylene) hydrogen atom attached to each carbon atom.
9.5.2 Structure of Benzene
Benzene was isolated by Michael Faraday
in 1825. The molecular formula of benzene,
C6H6, indicates a high degree of unsaturation.
This molecular formula did not account for
its relationship to corresponding alkanes,
alkenes and alkynes which you have studied
in earlier sections of this unit. What do you The Kekulé structure indicates
think about its possible structure? Due to the possibility of two isomeric
its unique properties and unusual stability, 1, 2-dibromobenzenes. In one of the isomers,
it took several years to assign its structure. the bromine atoms are attached to the
Benzene was found to be a stable molecule doubly bonded carbon atoms whereas in the
and found to form a triozonide which indicates other, they are attached to the singly bonded
the presence of three double bonds. Benzene carbons.

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320 chemistry

unhybridised p orbital perpendicular to the

plane of the ring as shown below:

However, benzene was found to form only

one ortho disubstituted product. This problem
was overcome by Kekulé by suggesting the
concept of oscillating nature of double bonds
in benzene as given below.

The unhybridised p orbital of carbon atoms

are close enough to form a π bond by lateral
overlap. There are two equal possibilities of
Even with this modification, Kekulé
forming three π bonds by overlap of p orbitals
structure of benzene fails to explain unusual
of C1 –C2, C3 – C4, C5 – C6 or C2 – C3, C4 – C5,
stability and preference to substitution
C6 – C1 respectively as shown in the following
reactions than addition reactions, which
figures.
could later on be explained by resonance.
Resonance and stability of benzene
According to Valence Bond Theory, the
concept of oscillating double bonds in benzene
is now explained by resonance. Benzene is a
hybrid of various resonating structures. The
two structures, A and B given by Kekulé are
the main contributing structures. The hybrid
structure is represented by inserting a circle
or a dotted circle in the hexagon as shown
in (C). The circle represents the six electrons
which are delocalised between the six carbon Fig. 9.7 (a)
atoms of the benzene ring.

(A) (B) (C)

The orbital overlapping gives us better
picture about the structure of benzene. All
2
the six carbon atoms in benzene are sp
2
hybridized. Two sp hybrid orbitals of each
2
carbon atom overlap with sp hybrid orbitals
of adjacent carbon atoms to form six C—C
sigma bonds which are in the hexagonal
2 Fig. 9.7 (b)
plane. The remaining sp hybrid orbital of
each carbon atom overlaps with s orbital Structures shown in Fig. 9.7(a) and (b)
of a hydrogen atom to form six C—H sigma correspond to two Kekulé’s structure with
bonds. Each carbon atom is now left with one localised π bonds. The internuclear distance

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Unit 9.indd 320 11/10/2022 15:29:07

Hydrocarbons 321

between all the carbon atoms in the ring has (i) Planarity
been determined by the X-ray diffraction to (ii) Complete delocalisation of the π electrons
be the same; there is equal probability for the in the ring
p orbital of each carbon atom to overlap with
(iii) Presence of (4n + 2) π electrons in the ring
the p orbitals of adjacent carbon atoms [Fig.
where n is an integer (n = 0, 1, 2, . . .).
9.7 (c)]. This can be represented in the form
of two doughtnuts (rings) of electron clouds This is often referred to as Hückel Rule.
[Fig. 9.7 (d)], one above and one below the Some examples of aromatic compounds are
plane of the hexagonal ring as shown below: given below:

(electron cloud)

Fig. 9.7 (c) Fig. 9.7 (d)

The six π electrons are thus delocalised
and can move freely about the six carbon
nuclei, instead of any two as shown in
Fig. 9.6 (a) or (b). The delocalised π electron cloud
is attracted more strongly by the nuclei of the
carbon atoms than the electron cloud localised
between two carbon atoms. Therefore, presence
of delocalised π electrons in benzene makes
it more stable than the hypothetical
cyclohexatriene.
X-Ray diffraction data reveals that benzene
is a planar molecule. Had any one of the above
structures of benzene (A or B) been correct,
9.5.4 Preparation of Benzene
two types of C—C bond lengths were expected.
However, X-ray data indicates that all the Benzene is commercially isolated from coal
six C—C bond lengths are of the same order tar. However, it may be prepared in the
(139 pm) which is intermediate between laboratory by the following methods.
C— C single bond (154 pm) and C—C double (i) Cyclic polymerisation of ethyne:
bond (133 pm). Thus the absence of pure (Section 9.4.4)
double bond in benzene accounts for the (ii) Decarboxylation of aromatic acids:
reluctance of benzene to show addition Sodium salt of benzoic acid on heating
reactions under normal conditions, thus with sodalime gives benzene.
explaining the unusual behaviour of benzene.
9.5.3 Aromaticity
Benzene was considered as parent ‘aromatic’
compound. Now, the name is applied to all the
ring systems whether or not having benzene (9.70)
ring, possessing following characteristics.

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322 chemistry

(iii) Reduction of phenol: Phenol is reduced (ii) Halogenation: Arenes react with halogens
to benzene by passing its vapours over in the presence of a Lewis acid like anhydrous
heated zinc dust FeCl3, FeBr3 or AlCl3 to yield haloarenes.

(9.71) Chlorobenzene
9.5.5 Properties (9.73)
Physical properties (iii) Sulphonation: The replacement of a
Aromatic hydrocarbons are non- polar hydrogen atom by a sulphonic acid group in
molecules and are usually colourless liquids a ring is called sulphonation. It is carried out
or solids with a characteristic aroma. You are by heating benzene with fuming sulphuric
also familiar with naphthalene balls which are acid (oleum).
used in toilets and for preservation of clothes
because of unique smell of the compound
and the moth repellent property. Aromatic
hydrocarbons are immiscible with water but
are readily miscible with organic solvents.
They burn with sooty flame.
Chemical properties (9.74)
Arenes are characterised by electrophilic
substitution reactions. However, under (iv) Friedel-Crafts alkylation reaction:
special conditions they can also undergo When benzene is treated with an alkyl halide
addition and oxidation reactions. in the presence of anhydrous aluminium
chloride, alkylbenene is formed.
Electrophilic substitution reactions
The common electrophilic substitution
reactions of arenes are nitration, halogenation,
sulphonation, Friedel Craft’s alkylation and
acylation reactions in which attacking reagent
+
is an electrophile (E )
(i) Nitration: A nitro group is introduced (9.75)
into benzene ring when benzene is heated
with a mixture of concentrated nitric acid
and concentrated sulphuric acid (nitrating
mixture).
(9.76)

Why do we get isopropyl benzene on

treating benzene with 1-chloropropane
instead of n-propyl benzene?

(v) Friedel-Crafts acylation reaction: The

reaction of benzene with an acyl halide or
(9.72) acid anhydride in the presence of Lewis acids
(AlCl3) yields acyl benzene.
Nitrobenzene

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Unit 9.indd 322 12/13/2022 10:16:03

Hydrocarbons 323

(9.77)

In the case of nitration, the electrophile,

nitronium ion, is produced by transfer of
a proton (from sulphuric acid) to nitric acid
in the following manner:
(9.78) Step I
If excess of electrophilic reagent is used,
further substitution reaction may take place
in which other hydrogen atoms of benzene Step II
ring may also be successively replaced
by the electrophile. For example, benzene
on treatment with excess of chlorine in
the presence of anhydrous AlCl 3 can be Protonated Nitronium
chlorinated to hexachlorobenzene (C6Cl6) nitric acid ion
It is interesting to note that in the process
of generation of nitronium ion, sulphuric acid
serves as an acid and nitric acid as a base.
Thus, it is a simple acid-base equilibrium.
(b) F o r m a t i o n o f C a r b o c a t i o n
(arenium ion): Attack of electrophile
results in the formation of σ-complex or
(9.79) arenium ion in which one of the carbon is sp
3

Mechanism of electrophilic substitution hybridised.

reactions:
According to experimental evidences, SE (S =
substitution; E = electrophilic) reactions are
supposed to proceed via the following three
steps:
(a) Generation of the eletrophile sigma complex (arenium ion)
(b) Formation of carbocation intermediate The arenium ion gets stabilised by
(c) Removal of proton from the carbocation resonance:
intermediate
⊕
(a) Generation of electrophile E : During
chlorination, alkylation and acylation of
benzene, anhydrous AlCl3, being a Lewis acid
⊕ ⊕
helps in generation of the elctrophile Cl , R ,
⊕
RC O (acylium ion) respectively by combining
with the attacking reagent.

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Unit 9.indd 323 12/1/2022 11:04:17

324 chemistry

Sigma complex or arenium ion loses its chemical equation:

aromatic character because delocalisation of
3 CxHy + (x + ) O2 → x CO2 + H2O n (9.83)
electrons stops at sp hybridised carbon.
(c) Removal of proton: To restore the 9.5.6 Directive influence of a functional
aromatic character, σ -complex releases group in monosubstituted benzene
3
proton from sp hybridised carbon on attack
– When monosubstituted benzene is subjected
by [AlCl4] (in case of halogenation, alkylation
– to further substitution, three possible
and acylation) and [HSO 4 ] (in case of
disubstituted products are not formed in
nitration).
equal amounts. Two types of behaviour are
observed. Either ortho and para products or
meta product is predominantly formed. It
has also been observed that this behaviour
depends on the nature of the substituent
already present in the benzene ring and not
on the nature of the entering group. This is
known as directive influence of substituents.
Reasons for ortho/para or meta directive
nature of groups are discussed below:
Addition reactions
Ortho and para directing groups: The
Under vigorous conditions, i.e., at high
groups which direct the incoming group to
temperature and/ or pressure in the presence
ortho and para positions are called ortho and
of nickel catalyst, hydrogenation of benzene para directing groups. As an example, let us
gives cyclohexane. discuss the directive influence of phenolic
(–OH) group. Phenol is resonance hybrid of
following structures:

Cyclohexane
(9.80)
Under ultra-violet light, three chlorine
molecules add to benzene to produce benzene
hexachloride, C6H6Cl6 which is also called
gammaxane.

Benzene hexachloride,
It is clear from the above resonating
(BHC) structures that the electron density is more on
(9.81) o – and p – positions. Hence, the substitution
Combustion: When heated in air, benzene takes place mainly at these positions. However,
burns with sooty flame producing CO2 and it may be noted that –I effect of – OH group also
H2O operates due to which the electron density on
15 ortho and para positions of the benzene ring
C H6 + O2 → 6CO2 +3H2O is slightly reduced. But the overall electron
6 2 (9.82) density increases at these positions of the
General combustion reaction for any ring due to resonance. Therefore, –OH group
hydrocarbon may be given by the following activates the benzene ring for the attack by

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Unit 9.indd 324 10/10/2022 10:38:01 AM

Hydrocarbons 325

an electrophile. Other examples of activating In this case, the overall electron density
groups are –NH2, –NHR, –NHCOCH3, –OCH3, on benzene ring decreases making further
–CH3, –C2H5, etc. substitution difficult, therefore these groups
In the case of aryl halides, halogens are are also called ‘deactivating groups’. The
moderately deactivating. Because of their electron density on o – and p – position
strong – I effect, overall electron density on is comparatively less than that at meta
benzene ring decreases. It makes further position. Hence, the electrophile attacks on
substitution difficult. However, due to comparatively electron rich meta position
resonance the electron density on o– and resulting in meta substitution.
p – positions is greater than that at the
9.6 Carcinogenicity and Toxicity
m-position. Hence, they are also o – and p –
directing groups. Resonance structures of Benzene and polynuclear hydrocarbons
chlorobenzene are given below: containing more than two benzene rings
fused together are toxic and said to
possess cancer producing (carcinogenic)
property. Such polynuclear hydrocarbons
are formed on incomplete combustion of
organic materials like tobacco, coal and
petroleum. They enter into human body
and undergo various biochemical reactions
and finally damage DNA and cause cancer.
Some of the carcinogenic hydrocarbons are
given below (see box).

Meta directing group: The groups which

direct the incoming group to meta position are
called meta directing groups. Some examples
of meta directing groups are –NO2, –CN, –CHO,
–COR, –COOH, –COOR, –SO3H, etc.
Let us take the example of nitro group.
Nitro group reduces the electron density in
the benzene ring due to its strong–I effect.
Nitrobenzene is a resonance hybrid of the
following structures.

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Unit 9.indd 325 10/10/2022 10:38:01 AM

326 chemistry

SUMMARY

Hydrocarbons are the compounds of carbon and hydrogen only. Hydrocarbons are mainly
obtained from coal and petroleum, which are the major sources of energy. Petrochemicals
are the prominent starting materials used for the manufacture of a large number of
commercially important products. LPG (liquefied petroleum gas) and CNG (compressed
natural gas), the main sources of energy for domestic fuels and the automobile industry, are
obtained from petroleum. Hydrocarbons are classified as open chain saturated (alkanes)
and unsaturated (alkenes and alkynes), cyclic (alicyclic) and aromatic, according to their
structure.
The important reactions of alkanes are free radical substitution, combustion, oxidation
and aromatization. Alkenes and alkynes undergo addition reactions, which are mainly
electrophilic additions. Aromatic hydrocarbons, despite having unsaturation, undergo
mainly electrophilic substitution reactions. These undergo addition reactions only under
special conditions.
Alkanes show conformational isomerism due to free rotation along the C–C sigma
bonds. Out of staggered and the eclipsed conformations of ethane, staggered conformation
is more stable as hydrogen atoms are farthest apart. Alkenes exhibit geometrical
(cis-trans) isomerism due to restricted rotation around the carbon–carbon double bond.
Benzene and benzenoid compounds show aromatic character. Aromaticity, the
property of being aromatic is possessed by compounds having specific electronic structure
characterised by Hückel (4n+2)π electron rule. The nature of groups or substituents attached
to benzene ring is responsible for activation or deactivation of the benzene ring towards
further electrophilic substitution and also for orientation of the incoming group. Some of
the polynuclear hydrocarbons having fused benzene ring system have carcinogenic property.

EXERCISES

9.1 How do you account for the formation of ethane during chlorination of methane ?
9.2 Write IUPAC names of the following compounds :
(a) CH3CH=C(CH3)2 (b) CH2=CH-C≡C-CH3

(c) (d) –CH2–CH2–CH=CH2

(f) CH3(CH2)4 CH (CH2)3 CH3

(e) CH2 –CH (CH3)2

(g) CH3 – CH = CH – CH2 – CH = CH – CH – CH2 – CH = CH2
|
C2H5
9.3 For the following compounds, write structural formulas and IUPAC names for all
possible isomers having the number of double or triple bond as indicated :
(a) C4H8 (one double bond) (b) C5H8 (one triple bond)
9.4 Write IUPAC names of the products obtained by the ozonolysis of the following
compounds :
(i) Pent-2-ene (ii) 3,4-Dimethylhept-3-ene
(iii) 2-Ethylbut-1-ene (iv) 1-Phenylbut-1-ene

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Hydrocarbons 327

9.5 An alkene ‘A’ on ozonolysis gives a mixture of ethanal and pentan-3-one.

Write structure and IUPAC name of ‘A’.
9.6 An alkene ‘A’ contains three C – C, eight C – H σ bonds and one C – C π
bond. ‘A’ on ozonolysis gives two moles of an aldehyde of molar mass 44
u. Write IUPAC name of ‘A’.
9.7 Propanal and pentan-3-one are the ozonolysis products of an alkene? What
is the structural formula of the alkene?
9.8 Write chemical equations for combustion reaction of the following
hydrocarbons:
(i) Butane (ii) Pentene
(iii) Hexyne (iv) Toluene
9.9 Draw the cis and trans structures of hex-2-ene. Which isomer will have
higher b.p. and why?
9.10 Why is benzene extra ordinarily stable though it contains three double
bonds?
9.11 What are the necessary conditions for any system to be aromatic?
9.12 Explain why the following systems are not aromatic?

(i) (ii) (iii)

9.13 How will you convert benzene into
(i) p-nitrobromobenzene (ii) m- nitrochlorobenzene
(iii) p - nitrotoluene (iv) acetophenone?
9.14 In the alkane H3C – CH2 – C(CH3)2 – CH2 – CH(CH3)2, identify 1°,2°,3° carbon
atoms and give the number of H atoms bonded to each one of these.
9.15 What effect does branching of an alkane chain has on its boiling point?
9.16 Addition of HBr to propene yields 2-bromopropane, while in the presence
of benzoyl peroxide, the same reaction yields 1-bromopropane. Explain
and give mechanism.
9.17 Write down the products of ozonolysis of 1,2-dimethylbenzene (o-xylene).
How does the result support Kekulé structure for benzene?
9.18 Arrange benzene, n-hexane and ethyne in decreasing order of acidic
behaviour. Also give reason for this behaviour.
9.19 Why does benzene undergo electrophilic substitution reactions easily and
nucleophilic substitutions with difficulty?
9.20 How would you convert the following compounds into benzene?
(i) Ethyne (ii) Ethene (iii) Hexane
9.21 Write structures of all the alkenes which on hydrogenation give
2-methylbutane.
9.22 Arrange the following set of compounds in order of their decreasing relative
+
reactivity with an electrophile, E
(a) Chlorobenzene, 2,4-dinitrochlorobenzene, p-nitrochlorobenzene
(b) Toluene, p-H3C – C6H4 – NO2, p-O2N – C6H4 – NO2.
9.23 Out of benzene, m–dinitrobenzene and toluene which will undergo nitration
most easily and why?
9.24 Suggest the name of a Lewis acid other than anhydrous aluminium chloride
which can be used during ethylation of benzene.
9.25 Why is Wurtz reaction not preferred for the preparation of alkanes
containing odd number of carbon atoms? Illustrate your answer by taking
one example.

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Rationalised 2023-24

Unit 9.indd 327 10/10/2022 10:38:02 AM