CHAPTER -13

HYDROCARBONS

The term ‘hydrocarbon’ means compounds of carbon and hydrogen only.

ALKANES
Alkanes are saturated open chain hydrocarbons containing carbon - carbon single
bonds. 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)

Preparation
1. From unsaturated hydrocarbons
Dihydrogen gas adds to alkenes and alkynes in the presence of finely divided
catalysts like platinum, palladium or nickel to form alkanes. This process is
called hydrogenation.

2. From alkyl halides

i) Alkyl halides (except fluorides) on reduction with zinc and dilute hydrochloric
acid give alkanes.

ii) Wurtz reaction: Alkyl halides on treatment with sodium metal in dry ethereal
(free from moisture) solution give higher alkanes. This reaction is known as

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Wurtz reaction and is used for the preparation of higher alkanes containing even
number of carbon atoms.

3. From carboxylic acids

i) Sodium salts of carboxylic acids on heating with soda lime (mixture of sodium
hydroxide and calcium oxide) give alkanes containing one carbon atom less than
the carboxylic acid. This process of elimination of carbon dioxide from a
carboxylic acid is known as decarboxylation.

ii) Kolbe’s electrolytic method: An aqueous solution of sodium or potassium salt

of a carboxylic acid on electrolysis gives alkane containing even number of
carbon atoms at the anode. [ 2(n-1) no. of carbon atoms in the product]

Electrolysis

Physical properties
Alkanes are almost non-polar molecules because of the covalent nature of C-C
and C-H bonds and due to very little difference of electronegativity between
carbon and hydrogen atoms. They possess weak van der Waals forces.
1. Solubility: It is generally observed that in relation to solubility of substances in
solvents, polar substances are soluble in polar solvents, whereas the non-polar
ones in non-polar solvents.
2. Boiling point: Boiling point of alkanes increases with increase in molecular
mass due to increase in intermolecular Vanderwaal’s forces. With increase in
number of branched chains, the boiling point decreases. As branching increases
the molecule attains the shape of a sphere which result in smaller area of contact
and therefore, weak intermolecular forces between them. Hence, the boiling point
decreases with increase in branching in alkanes.
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Chemical properties

1. Substitution reactions
One or more hydrogen atoms of alkanes can be replaced by halogens, nitro group
and sulphonic acid group. Halogenation takes place either at higher temperature
(573-773 K) or in the presence of diffused sunlight or ultraviolet light. These
reactions in which hydrogen atoms of alkanes are substituted are known as
substitution reactions.

2. Combustion
Alkanes on heating in the presence of air or dioxygen are completely oxidized to
carbon dioxide and water with the evolution of large amount of heat.

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

4. Isomerisation
n-Alkanes on heating in the presence of anhydrous aluminium chloride and
hydrogen chloride gas isomerise to branched chain alkanes.
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5. Aromatization
n-Alkanes having six or more carbon atoms on heating to 773K at 10-20
atmospheric pressure in the presence of oxides of vanadium, molybdenum or
chromium supported over alumina get dehydrogenated and cyclised to benzene
and its homologues. This reaction is known as aromatization or reforming.

6. Reaction with steam

Methane reacts with steam at 1273 K in the presence of nickel catalyst to form
carbon monoxide and dihydrogen. This method is used for industrial preparation
of dihydrogen gas.

7. Pyrolysis
Higher alkanes on heating to higher temperature decompose into lower alkanes,
alkenes etc. Such a decomposition reaction into smaller fragments by the
application of heat is called pyrolysis or cracking.

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CONFORMATIONS
1. The spacial arrangement of atoms which can be converted into one another by
rotation around a C-C single bond are called conformations or conformers or
rotamers.
2. Rotation around C-C single bond is not completely free and it is hindered due
to weak repulsive interaction between the adjacent bonds. Such type of
repulsive interaction is called torsional strain.
3. Conformations of ethane : Ethane molecule contains C-C single bond which
on rotation results into infinite number of spacial arrangement of hydrogen
atoms attached to carbon atoms.
The conformation of ethane in which hydrogen atoms attached to 2 carbon are
as close as possible is called eclipsed conformation. The conformation of
ethane is which hydrogen atoms attached to two carbon atoms are as far apart
a possible is called staggered conformation. The other conformations of
ethane are called skew conformations.

I .Sawhorse projections

II. Newman projections

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ALKENES
Alkenes are also known as olefins (oil forming) since the first member, ethylene or ethene
(C2H4) was found to form an oily liquid on reaction with chlorine.
Geometrical Isomerism
The compounds which possess the same structural formula but differ in the spacial
arrangement of groups about C=C carbon-carbon double bond are called geometrical
isomers.
Cis Isomer- The isomer in which two identical atoms or groups lie on the same side of
double bond is called cis isomer.
Trans Isomer- The isomer in which the two identical atoms or groups lie on the opposite
side of double bod is called trans isomer.
Example:

PREPARATION OF ALKENES:
1. From alkynes: Alkynes on partial reduction with calculated amount of dihydrogen in the
presence of palladised charcoal give alkene. Partially deactivated palladised charcoal is
known as Lindlar’s catalyst. Alkenes thus obtained are having cis geometry. However,
alkynes on reduction with sodium in liquid ammonia form trans alkenes.

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2. From alkyl halides: Alkyl halides (R-X) on heating with alcoholic potash (potassium
hydroxide dissolved in alcohol, say, ethanol) eliminate one molecule of halogen acid to form
alkenes. This reaction is known as dehydrohalogenation i.e., removal of halogen acid. This is
example of ᵦ -elimination reaction, since hydrogen atom is eliminated from the ᵦ carbon
atom.

3. From vicinal dihalides: Dihalides in which two halogen atoms are attached to two
adjacent carbon atoms are known as vicinal dihalides. Vicinal dihalides on treatment with
zinc metal lose a molecule of ZnX2 to form an alkene. This reaction is known as
dehalogenation.

4. From alcohols by acidic dehydration: Alcohols on heating with concentrated sulphuric

acid form alkenes with the elimination of one water molecule. Since a water molecule is
eliminated from the alcohol molecule in the presence of an acid, this reaction is known as
acidic dehydration of alcohols. This reaction is also the example of ᵦ-elimination reaction
since –OH group takes out one hydrogen atom from the ᵦ -carbon atom.

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Physical properties of alkens
1. Solublity: Ethene is a colourless gas with a faint sweet smell. All other alkenes are
colourless and odourless, insoluble in water but fairly soluble in nonpolar solvents like
benzene, petroleum ether.
2. Boiling point : They show a regular increase in boiling point with increase in size i.e.,
every – CH2 group added increases boiling point by 20–30 K. Like alkanes, straight chain
alkenes have higher boiling point than isomeric branched chain compounds.

Chemical properties:
1.Addition of halogens : Halogens like bromine or chlorine add up to alkene to form vicinal
dihalides. 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.

2. Addition of hydrogen halides: Hydrogen halides (HCl, HBr,HI) add up to alkenes to form
alkyl halides. The order of reactivity of the hydrogen halides is,
HI > HBr > HCl.
(i) Addition reaction of HBr to symmetrical alkenes
Addition reactions of HBr to symmetrical alkenes (similar groups attached to double bond)
take place by electrophilic addition mechanism.

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(ii) Addition reaction of HBr to unsymmetrical alkenes (Markovnikov Rule)
Markovnikov rule states that during the addition of hydrogen halide to unsymmetrical
alkene, the negative part of the addendum (adding molecule) gets attached to that carbon
atom which possesses lesser number of hydrogen atoms.

3. 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 is known as peroxide effect or Kharash effect.
This happens only with HBr but not with HCl and Hl.

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

5. 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.

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6.Ozonolysis : Ozonolysis of alkenes involves the addition of ozone molecule to alkene to
form ozonide, and then cleavage of the ozonide by Zn-H2O to smaller molecules. This
reaction is highly useful in detecting the position of the double bond in alkenes or other
unsaturated compounds.

7.Polymerisation: Polythene is obtained by the combination of large number of ethene

molecules at high temperature, high pressure and in the presence of a catalyst. The large
molecules thus obtained are called polymers. This reaction is known as polymerisation. The
simple compounds from which polymers are made are called monomers. Other alkenes also
undergo polymerisation.

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ALKYNES

Preparation of alkynes:
1. From calcium carbide: On industrial scale, ethyne is prepared by treating calcium carbide
with water. Calcium carbide is prepared by heating quick lime with coke.

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

hydroxide undergo dehydrohalogenation. One molecule of hydrogen halide is eliminated to
form alkenyl halide which on treatment with sodamide gives alkyne.

Physical properties
1. They are lighter than water and immiscible with water but soluble in organic solvents like
ethers, carbon tetrachloride and benzene.
2. Their melting point, boiling point and density increase with increase in molar mass.

Chemical properties
1. Acidic character of alkyne:
Sodium metal and sodamide (NaNH2) are strong bases. They react with ethyne to form
sodium acetylide with the liberation of dihydrogen gas. These reactions have not been
observed in case of ethene and ethane thus indicating that ethyne is acidic in nature in
comparison to ethene and ethane.
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Reason for acidity:
Due to the maximum percentage of s character (50%), the sp hybridised orbitals of carbon
atoms in ethyne molecules have highest electronegativity; hence, these attract the shared
electron pair of the C-H bond of ethyne to a greater extent than that of the sp2 hybridised
orbitals of carbon in ethene and the sp3 hybridised orbital of carbon in ethane. Thus in
ethyne, hydrogen atoms can be liberated as protons more easily as compared to ethene and
ethane.

2. Addition of dihydrogen:

3. Addition of halogens:

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Reddish orange colour of the solution of bromine in carbon tetrachloride is decolourised.
This is used as a test for unsaturation.

4. Addition of hydrogen halides: Two molecules of hydrogen halides (HCl, HBr, HI) add
to alkynes to form gem dihalides (in which two halogens are attached to the same carbon
atom)

5.Addition of water: (Kucherov’s reaction) One molecule of water adds to alkynes on

warming with mercuric sulphate and dilute sulphuric acid at 333 K to form carbonyl
compounds.

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6. Cyclic polymerisation: Ethyne on passing through red hot iron tube at 873K undergoes
cyclic polymerization. Three molecules polymerise to form benzene, which is the starting
molecule for the preparation of derivatives of benzene, dyes, drugs and large number of other
organic compounds.

AROMATIC HYDROCARONS
1. The hydrocarbons which possess pleasant odour are named as Aromatic compounds.
These hydrocarbons are also known as Arenes.
2. Benzene is a very common and simplest aromatic hydrocarbon.
3. Aromatic compounds containing benzene ring are called benzenoid compounds where as
the one which do not contain benzene ring are known as non-benzenoid compounds.

AROMATICITY
For a compound to be aromatic, it should possess the following characteristics.
(i) Planarity.
(ii) Complete delocalisation of ℼ electrons in the ring.
(iii) Presence of (4n+2) ℼ electrons in the ring where n is a positive integer (n=0,1,2…)
This is referred as Huckel rule.

BENZENE
Preparation of benzene:
1. Decarboxylation of aromatic acids: Sodium salt of benzoic acid on heating with sodalime
gives benzene.

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2. Reduction of phenol: Phenol is reduced to benzene by passing its vapours over heated
zinc dust.

Physical properties
Aromatic hydrocarbons are non- polar molecules and are usually colourless liquids or solids
with a characteristic aroma.
Aromatic hydrocarbons are immiscible with water but are readily miscible with organic
solvents. They burn with sooty flame.
Chemical properties
I.Electrophilic substitution reactions
1. Nitration: A nitro group is introduced into benzene ring when benzene is heated with a
mixture of concentrated nitric acid and concentrated sulphuric acid (nitrating mixture).

2. Halogenation: Arenes react with halogens in the presence of a Lewis acid like anhydrous
FeCl3, FeBr3 or AlCl3 to yield haloarenes.

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3. Sulphonation: The replacement of a hydrogen atom by a sulphonic acid group in a ring is
called sulphonation. It is carried out by heating benzene with fuming sulphuric acid (oleum).

4. Friedel-Crafts alkylation reaction: When benzene is treated with an alkyl halide in the
presence of anhydrous aluminium chloride, alkyl benzene is formed.

5. Friedel-Crafts acylation reaction: The reaction of benzene with an acyl halide or acid
anhydride in the presence of Lewis acids (AlCl3) yields acyl benzene.

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6. Reaction with excess of chlorine: Benzene on treatment with excess of chlorine in the
presence of anhydrous AlCl3 can be chlorinated to hexachlorobenzene (C6Cl6).

II. ADDITION REACTIONS:

1. Addition of hydrogen: Under vigorous conditions, i.e., at high temperature and/ or
pressure in the presence of nickel catalyst, hydrogenation of benzene gives cyclohexane.

2. Addition of halogen: Under ultra-violet light, three chlorine molecules add to benzene to
produce benzene hexachloride, C6H6Cl6 which is also called gammaxane.

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