HYDROCARBONS

What Are Hydrocarbons?

HYDROCARBONS are the compounds

containing carbon and hydrogen only.
1.1 Classification Of
Hydrocarbon
Depending upon the types of carbon-carbon
bonds present, they can be classified into tree
main categories:

1) Saturated Hydrocarbon
2) Unsaturated Hydrocarbon
3) Aromatic Hydrocarbon
1.1.1Saturated Hydrocarbon
The hydrocarbon that contain only carbon-
carbon single bond is called Saturated
Hydrocarbon. These include open chain hydrocarbon as
well as closed chain hydrocarbons. These compounds are called
saturated because they have maximum number of bonded
hydrogen
If different carbon atoms are joined together to form an
open chain of carbon atoms with single bonds, they are called
Alkanes.
For example: 2-Methylpropane (Isobutane)

If carbon atoms form a closed chain or ring, they are called

Cycloalkanes.
For example: Cyclopentane
1.1.2 Unsaturated Hydrocarbon
The hydrocarbons which contain carbon-
carbon multiple bond (Double bonds or
triple bond) are called unsturated
hydrocarbon.
Depending upon multiple bond they are further
classified as alkenes and alkynes.
o Alkenes : These are hydrocarbon which contain at least one
carbon-carbon bond. For example: Ethene

o Alkynes: These are hydrocarbons which contain at least one

carbon-carbon triple bond. For example: Ethyne
1.1.3 Aromatic hydrocarbon
The hydrocarbons which contain at least one special type of
hexagonal ring of carbon atoms with three double bond in the
alternate positions are called aromatic hydrocarbon. The ring is
called aromatic ring.

For example: i) Toluene ii) o-Xylene

The aromatic compounds may also contain more than one

benzene rings.
For example: i) Naphthalene ii) Anthracene
The type of Hydrocarbon can be
summarized as :
Hydrocarbon Characteristic
Type Group Example
CH3CH2CH3
Saturated No double or Triple Bond
Hydrocarbon: Propane

Alkanes
CH3–CH═CH2
Unsaturated Double Bond Propene
Hydrocarbon:
Alkenes CH3−C≡CH

Triple Bond Propyne

Alkynes

Aromatic Benzene ring Methyl Benzene

Hydrocarbons:
ALKANES
1.2 Alkanes
Alkanes are saturated hydrocarbon containing
only carbon-carbon single bond in their
molecule. They are also called Paraffins. At high
temperatures and pressure do undergo some
reaction. The alkanes may be divided as:

1) Open chain or Acyclic alkanes

2) Cycloalkanes or cyclic alkanes
1.2.1 Open chain Or Acyclic
alkanes
These are simple alkanes without any
close chains and have the general
formula where CnH2n + 2 n is the number of
carbon atoms.

For example: i) Methane - CH4

1.2.2 Cycloalkanes Or Cyclic
alkanes
These contain a closed chain or ring in their molecules. They
have the general formula CnH2n.

For example: i) Cyclopropane- or

ii)Cyclobutane- or
1.3 Structure Of Alkanes
Methane is the first member of the family. It has
Tetrahedral Structure involving sp3 Hybridisation.
The four sigma bond is formed by the overlapping of
sp3 hybrid orbitals of carbon and 1s orbital of
hydrogen. In this, carbon atom lies at the centre and
the four hydrogen atoms lies at the corners of a
regular tetrahedron. Making H-C-H bond angle of
109.5˚.

a) b)
1.4 Nomenclature Of
Alkanes
Nomenclature implies assigning proper name to the basis of
certain standard rules so that the study of these compounds may
become standard. The rules for naming them are as follows:

i) Longest Chain Rule

select the longest continues chain of carbon
First of all,
atoms in a molecule.
1 2 3 4 5 6 7 8 9
For eg. CH3– CH– CH2– CH2– CH2–CH– CH2– CH2–CH3

CH3 CH2−CH3

In the example ,the longest chain has nine carbons and it is

considered as parent root chain and carbon atoms which are
not included in parent chain are called substituents.
ii)Position of the substituent
The carbon atoms of the parent chain are
numbered to identify the parent alkane and to
locate the positions of the carbon atom at
which branching take place due to the
substitution of alkyl group in place of hydrogen
atom. The numbering is done in such a way that
the branched carbon atoms get the lowest possible
number.

For eg: 9 8 7 6 5 4 3 2 1
C−C−C−C−C−C−C−C−C

C C−C
iii) Lowest set of locants

When two or more substituents are present, then end of the

parent chain which gives the lowest set of the locants is
preferred for numbering. This rule is called lowest set of
locants.
This means that when two or more different sets
of locants are possible, that set of locants which when
compared term with other sets, each in order of increasing
magnitude, has the lowest term at the first point of
difference.

For eg: 6 5 4 3 2 1

H3C−CH−CH3−CH−CH−CH3

CH3 CH3 CH3

Set of locants: 2,3,5

iv) Presence of more than one same substituent.

If the same substituent or side chain occurs more

than once, the prefix di(for 2), tri(for 3), tetra(for
4), penta(for 5),hexa(for 6)…etc., are attached to
the names of the substituents. The positions of the
substituents are indicated separately and the
numerals representing their positions are separated
by commas.

For eg: 1 2 3 4 5
CH3–CH–CH2–CH–CH3

CH3 CH3

2,4-Dimethylpentane
v)Naming different substituents

If two or more different substituents or side chains

are present in the molecule, they are named in the
alphabetical order along with their appropriate
positions. Prefix are ignored while comparing the
substituents.

For eg: CH2CH3

5 4 3 2 1
CH3−CH3−C−CH3−CH3

CH3CH3

3 -Ethyl-2,3-dimethylpentane
vi) Naming different substituents at equivalent positions
If two different substituents are in equivalent positions
from the two ends of the chain, then the numbering of
the chain is done in such a way that the group which
comes first in the alphabetical order gets lower down.
For eg: 1 2 3 4 5 6 7 7 6 5 4 3 2
1
CH3−CH2−CH−CH2−CH−CH2−CH3 CH3−CH2−CH−CH2−CH−CH2−CH3

CH3 CH2CH3 CH 3 CH2CH3

( Methyl at C-3) (Ethyl at C-3)

The carbon bearing ethyl group gets lower position because it is cited
first in the name according to alphabetical order of substituents. So
correct name of compound is :3-Ethyl-5-methylheptane
CH3−CH2−CH−CH2−CH2−CH− CH2 −CH3
(3-Ethyl-6-
methyloctane)
CH2CH3 CH3
vii)Naming the complex substituents (or substituted
substituents)

If the substituent on the parent chain is complex it is named as

substituted alkyl group by numbering the carbon atom of this
group attached to the parent chain.
The name of such substituents is given in brackets in order to
avoid confusion with the numbering of the parent chain.
For eg:
1.5 Preparation of
Alkanes
Petroleum and natural gas are the main source
of alkanes. However, alkanes can be prepared
by three methods.
Methods for
preparation of
alkanes

From
unsaturated
From alkyl From carboxylic
hydrocarbon halides acids
1.5.1 From Unsaturated Hydrocarbon
The unsaturated hydrocarbons (alkenes and alkynes) are
converted into alkanes by catalytic hydrogenation. In this
process dihydrogen is passed through alkenes or alkynes in
the presence of finely divided catalysts such as Raney Ni, Pt
or Pd. These metals absorb dihydrogen gas on their
surfaces and activate the hydrogen-hydrogen bond.
Platinum and palladium catalyse the reaction at room
tempreture. However,higher temperature (523-573k) and
pressure are required with nickle catalysts.
The hydrogenation reaction of unsaturated
hydrocarbon using nickel at a tempreture of 523-573K is
commonly known as Sabatier and Sender’s reaction or
reduction.
Methane cannot be prepared by this
method because starting alkene or alkyne must contain at
least two carbon atom.

For eg:
1.5.2 From alkyl halides
i) Alkyl halides (except fluorides) on reduction with zinc
and dilute hydrochloric
acid give alkanes.
For eg:

ii) Alkyl halides on treatment with sodium metal in dry

ethereal (free from moisture)solution give higher
alkanes. This reaction is known as Wurtz reaction
and is used for the preparation of higher alkanes
containing even number of carbon atom.

For eg:
1.5.3 From Carboxylic
acids
From carboxylic
acid

Decarboxylation Kolbe’s electrolytic

reaction method

i) Decarboxylation reaction :
Sodium salts of carboxylic acids on heating with soda
lime (mixture of sodium hydroxide and calcium
oxide)gives 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.
For eg:
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.

The reaction is supposed to follow the following path:

 .

i)

ii)At anode:

iii)

iv)At cathode:
1.6 Properties of Alkanes
Properties

Physical properties Chemical properties

1.6.1 Physical Properties

Nature
Alkanes are almost non-polar molecules and therefore
the molecules are held only by weak Van der Waals forces.
The weak intermolecular forces depend only upon the size
and the structure of the molecule. Due to weak forces, the C1
to C4 are gases, the next thirteen alkanes from C5 to C17 are
liquid and the higher member with more than 18 carbon
atoms are solid at 298 K.
 Boiling Point
Alkanes have generally low boiling points because these
are non-polar and the molecules are held together only by
weak Van der Waals’ forces. With the increase in the
number of carbon atoms, the molecular size increases and
therefore, the magnitude of Van der Waals forces also
increases. Consequently, the boiling points increase with
increase in number of carbon atoms.
It has been observed that each carbon
added to the chain increases the boiling point by 20-30 k.
the boiling point of n-alkanes with increase in number of
carbon per molecule of the homologous series.

Variations of boiling point of alkane with increase in

Boiling Point

• Among the isomeric alkanes, the branched chain isomer will

have lower boiling point than the corresponding straight
chain compound.
• This is because surface area decreases due to which vander
Waal's forces decreases.
• Greater the branched chain, lower the boiling point.
Melting point

The melting points of alkanes do not shows regular

variation with increase in molecular size. It has been
observed that, in general, the alkanes with even number
of carbon atoms have higher melting points as compared
to the immediately next lower alkanes with odd number
of carbon atoms.
Alkane C 3H 8 C4H10 C5H12 C6H14 C7H16 C8H18

m.p.(K) 85.9 138 143.3 178.5 182.5 216.2

This is because the alkanes with even number of carbon

atoms have more symmetrical structures and result in
closer packing in the crystal structure as compared to
alkanes with odd number of carbon atoms. Therefore,
the attractive forces in the former are more and the
melting points are higher as compared to the alkanes
with odd number of carbon atoms.
Solubility
Alkanes being non-polar in nature, are expected to be
insoluble in water(polar solvent). They dissolve in non-
polar solvents such as ether, benzene, carbon
tetrachloride etc. The solubility generally decreases with
increase in molecular mass. As we know, petrol is a
mixture of hydrocarbon and is used as a fuel for
automobiles.

Density
Alkanes are lighter than water. The density increase with
the increase in the number of the carbon atoms.
1.6.2 Chemical
Properties
Substitution reaction
The reaction in which an atom or a group of
atoms in a molecule is replaced by some
other atom or group of atom. Alkanes
undergo substitution reaction in which one
or more hydrogen atoms are replaced or
substituted by different atoms or groups
such as halogen atom (Cl, Br or I), nitro
group(-NO2) or sulphonic acid (-SO3H)
group.
i ) Halogenation
This involves the replacement of one or more
atoms of alkanes by the corresponding number
of halogens atoms. It is found that the rate of
reaction of alkanes with halogen is
F2>Cl2>Br2>I2.
Rate of replacement of hydrogen of alkanes
is:3˚>2˚>1˚.
For eg:

Dichloromethane
IODINATION

Iodination of alkanes is a reversible process because HI formed as

the byproduct reduces iodomethane back to methane.
Thus, direct iodination is carried out by oxidizing reagents like
HNO3 and HIO3 because they will turn HI to I2.

FLUORINATION
Fluorination of alkanes is vigorous and explosive.
ii ) Mechanism
i) Initiation
The reaction is initiated by homolysis of chlorine molecule
in the presence of light or heat, the Cl-Cl bond is weaker
than the C-C and C-H bond and hence, is easiest to
break.

ii) Propagation
Chlorine free radicals attacks the methane molecule and
takes the reaction in the
forward direction by breaking the C-H bond to generate
methyl free radical with
the formation of H-Cl.

The methyl radical thus obtained attacks the second

molecule of chlorine to form
CH3-Cl with the liberation of another chlorine free radical
by homolysis of
iii) Termination

The reaction stops after some time due to consumption

of reactants and/or due to
following side reaction:
The possible chain terminating steps are:
a)
b)
c)

Though in (c) CH3-Cl, one of the product is formed but

free radicals are consumed and the chain is
terminated.
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.

The general combustion equation for any alkane is:

Due to the evolution of large amount of heat during

combustion, alkanes are used
as fuels
Incomplete combustion

• During incomplete combustion of alkanes with insufficient

amount of air or dioxygen, carbon black is formed which is
used in the manufacture of ink, printer ink, black pigments
and as filters.
Controlled Oxidation
Alkanes on heating with a regulated supply of dioxygen or
air at high pressure and in the presence of suitable
catalyst give a variety of oxidation product:
 Isomerisation
Alkane isomerise to branched chain alkanes when
heated with anhydrous aluminium chloride (AlCl 3) and
hydrogen chloride at 573 K under a pressure of about
30-35 atmosphere. CH 3

anhy.AlCl3,HCl
CH3CH2CH2CH3 CH3−CH−CH3
n-butane isobutane
Aromatization
The alkanes containing six or more carbon
atoms when heated at about 773K under high
pressure of 10-20 atm in the presence of oxides
of vanadium, molybdenum or chromium
supported over alumina get dehydrogenated
and cyclized to benzene and its homologues.
This process is called aromatization or
reforming.
Reaction with steam
On passing a mixture of steam and methane over heated
nickel (supported over alumina, Al2O3) catalyst at 1273 K,
methane is oxidised to carbon monoxide and hydrogen is
evolved.

Pyrolysis
When higher alkanes are heated to high temperature , the
alkanes break down to lower alkanes and alkenes. For
eg:
C3 H8 C2H4 + CH4 or C3H6 + H2
This reaction is called Fragmentation or Cracking or
Pyrolysis. Pyrolysis of hexane gives following product:
 Conformations
• The spatial arrangements of atoms which can be
converted into one another by rotation around a C-C
single bond are called conformations or conformers or
rotamers.
a) Eclipsed
• In eclipsed conformer, the e clouds of the C-H bonds are
closer to each other resulting in increase e cloud
repulsions.
• High energy due to greater repulsion(torsional strain)
between H-atoms.
• Less stable
b) Staggered
• In staggered conformer, the e clouds of the C-H bonds are far
apart as possible, resulting in minimum e cloud repulsions.
• Low energy due to less repulsion(less torsional strain) between
H-atoms.
• Maximum stability of the molecule
Any other intermediate conformation is called a skew
conformation.
Energy difference between the eclipsed and staggered
conformation in ethane molecule is 12.5 KJ/mol.
1.7 Conformation Of Ethane
Chemist represent conformations in two simple ways:
a)Sawhorse representation b)Newman projection
1.7.1 Sawhorse representation
In this projection, the molecule is viewed along the axis
of the model from an
oblique angle. The central carbon-carbon bond (C-C) s
drawn as a straight line
slightly tilted to right for the sake of clarity. The front
carbon is shown as the
lower left hand carbon and the rear carbon is shown as
the upper right hand
carbon.
A saw-horse or sawhorse is a beam with
four legs used to support a board or
plank for sawing
https://www.youtube.com/watch?v=jUqb-KD9SuY&t=1s
1.7.2 Newman Projection
In this method, the molecule is viewed from the front
along the carbon-carbon bond axis. The two carbon
atoms forming the σ bond are represented by two
circle; one behind the other so that only the front
carbon is seen. The front carbon atom is shown by a
point whereas the carbon further from the eye is
represented by the circle. Therefore, the C-H bonds of
the front carbon are depicted from the centre of the
circle while C-H bonds of the back carbon are drawn
from the circumference of the circle at an angle of 120˚
at each other.
https://www.youtube.com/watch?v=LHx4-Oqrur4
 https://www.youtube.com/watch?v=jUqb-KD9SuY&t=1s

• https://www.youtube.com/watch?v=LHx4-Oqrur4
Alkenes
1.8 Alkenes
Alkenes are unsaturated hydrocarbons containing
carbon-carbon double bond (C═C)in their molecules.
They have the general formula CnH2n. The simplest
member of alkene family is ethene, C2H4. The alkenes
are also called olefins (Greek olefiant meaning oil
forming) because the larger member of the series
(such as ethylene, propylene, etc react with chlorine to
form oily products.

Propene
1.9 Structure of Double
Bond
Carbon-Carbon double bond in alkenes consists of one
strong sigma(σ) bond (bond enthalpy about 397kJ mol-1
due to head on overlapping of sp2 hybridised orbitals
and one weak pi bond(bond enthalpy about 284 kJ mol-
1)obtained by lateral or sideways overlapping of the two
2p orbitals of the two carbon atom. The double bond is
shorter in bond length (134pm) than the single bond
(154pm). Alkenes are easily attacked by reagents or
compounds which are in search of electron (electrophilic
reagents)because they behave as source of loosely held
mobile electron. The presence of weaker pi bond makes
alkenes unstable molecules in comparison to alkanes
and thus, alkenes can be changed into single bond
compounds by combining with the electrophilic reagents.
1.10 Nomenclature
According to IUPAC system alkenes are named similar to alkanes
with the following modification:
i)The longest continues chain should include both the carbon
atoms of the double bond.
ii)The suffix used for alkene is –ene
iii)The chain is numbered from the end that gives the lower
number to the first carbon atom of the double bond.
iv)If there are two or more double bonds the ending ane of the
alkane is replaced by adiene or atiene.
1 2 3 4 5 1 2 3
4
For eg: CH3CH=CHCHCH3 CH2=CH−CH=CH2
Buta-1,3-diene

CH3
4-Methylpent-2-ene
1.11 Isomerism In
Alkenes
Isomerism in
Alkanes

Structural Geometrical
Isomerism Isomerism

Position
Chain Isomerism
Isomerism
1.11.1 Structural
Isomerism
Alkenes show following types of structural isomerisms:
i)Chain Isomerism
The isomers differ with respect to the chain of carbon atoms. as
in alkanes, ethene (C2H4) and propene(C3H6) can have only
one structure but alkenes higher than propene have different
structures.
For eg: 4 3 2 1
CH3−CH2−CH=CH2
But-1-ene
ii)Position Isomerism
The isomers differ in the position of the double bonds. For eg:
CH2=CH-CH2−CH3 (But-1-ene) CH3−CH=CH−CH3 (But-2-ene)
Structures I and III, and
II and III are the
examples of chain
isomerism whereas
structures I and II are
position isomers.
• 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 trans-but-2-ene is non-polar.
• In the trans-but-2-ene, the two methyl groups are in opposite
directions, therefore, dipole moments of C-CH3 bonds cancel, thus
making the trans form non-polar.
 Trans isomers have higher symmetry
compared to cis isomers, hence they
are tightly packed leading to higher
melting point compared to the cis
isomers.

Boiling point of cis isomers are higher

than trans isomers because cis isomers
are polar and hence they have strong
intermolecular forces between the
molecules.
Will propene show geometrical isomerism?
1.12 Preparation of Alkenes
From
Alkynes

From Alkyl
Halides
Preparati on
Of Alkenes
From Vicinal
Dihalides

From
Alcohols
1.12.1 From Alkynes
Alkynes can be reduced to alkenes using palladium
charcoal (palladised charcoal) catalyst partially
deactivated with poison like sulphur compounds or
quinoline. Partially deactivated palladised charcoal is
known as Lindlar’s catalyst. Alkynes can also be
reduced to alkenes with sodium in liquid ammonia
(called Birch reduction) to form trans alkenes.

For eg: CH3−C≡C−CH3 + H2 Pd/ C CH3CH═CHCH3

But-2-yne But-2-ene
CH3–C≡CH+H2 Pd/C CH3–CH=CH2
Propyne Propene
CH≡CH+H2 Pd/C CH2=CH2
Ethyne Ethene
Quinoline
Will propene show geometrical isomerism?
 1.12.2 From Alkyl Halides
Alkene can be prepared from alkyl halides(usually bromides
or iodides) by treating with alcoholic potash(potassium
hydroxide dissolved in ethanol). This reaction removes a
molecule of HX and therefore, the reaction is called
dehydrohalogenation. In this reaction, the hydrogen atom
is eliminated from β carbon atom (carbon atom next to the
carbon to which halogen is attached). Therefore, the
reaction is also called β–elimination reaction.

Nature of halogen atom and the alkyl group determine rate

of the reaction. It is observed that for halogens, the rate is:
Iodine>Bromine>Chlorine while for alkyl group it is
Tertiary> Secondary>Primary.
However, if the structure of alkyl halide is such
that it can undergo elimination in 2 different
ways, the preferred product is that alkene
which has a greater number of alkyl groups
attached to the doubly bonded carbon atoms.
Saytzeff's rule helps to determine the formation
of the major alkene in a dehydrohalogenation
reaction.
This is called Saytzeff rule.
1.12.3 From Vicinal
Dihalides
Dihalogen derivatives of alkanes in which two halogens atoms are
attached to adjacent carbon atoms (called vicinal dihalogen
derivatives) are converted to alkenes by heating with zinc dust in
ethyl alcohol. For eg:
CH3CHBr−CH2Br+Zn CH3CH=CH2+ZnBr2
CH2Br−CH2Br+Zn CH2=CH2+ZnBr2

1.12.4 From Alcohols

Alkenes are prepared from alcohols by heating with protonic acids
such as sulphuric acid at about 443K. This reaction is called
dehydration of alcohols
CH3CH2OH H SO
2 4 CH2=CH2+H2O

This reaction is also an example of β-elimination reaction because

–OH group takes out one hydrogen atom from the β- carbon
atom.
1.13 Properties Of Alkenes
1.13.1 Physical Properties
• Melting Point
In general, alkenes have higher melting point than the
corresponding alkanes. This is due to the reason that pi-
electrons of a double bond are more polarizable than s-electron
of single bonds. As a result, the intermolecular force of
attraction are stronger in alkenes than alkanes. The melting
and boiling point of alkenes in general, increase with increase
in molecular mass.

• Boiling Point
The boiling points of alkene show a regular gradation with the
increase in number of carbon atoms like alkanes. In general, for
each added –CH2 group the boiling point rises by 20˚-30˚.
• Dipole Moments
Alkenes are weakly polar. The pi-electron of the double bond can be
easily polarized. Therefore, their dipole moments are higher than
those of alkanes. The dipole moment of alkene depends upon the
position of the groups bonded to the two double bonded carbon
atoms. The symmetrical trans alkenes are non-polar and hence
have zero dipole moment. However, unsymmetrical trans-alkenes
have small dipole moment because the two dipoles opposes each
other but they do not cancel out each other exactly since they are
unequal. On the other hand, both symmetrical and asymmetrical
cis-alkenes are polar and hence have finite dipole moments. This
is because the two dipoles of individual bonds are on the same
side and hence have a resultant dipole moment.

• Solubility
Alkenes are lighter than water. These are insoluble in water
because they are non-polar. However, they readily dissolve in
organic solvents like alcohol, benzene, ether, carbon tetrachloride,
etc.
1.13.2 Chemical Properties
• Addition of dihydrogen
Alkenes add up on molecule of dihydrogen gas in the
presence of finally divided nickle, palladium or
platinum to form alkanes.
• 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. Addition of
halogen to alkene is an example of electrophilic
addition reaction.
 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. Like addition of
halogens to alkenes, addition of hydrogen halides

*is also an example of electrophilic addition

Markovnikov Rule
reaction
Markovnikov, a Russian chemist made a
generalisation in 1869. these generalisation
led Markovnikov to frame a rule call
Markovnikov rule. The rule stated that:
“During the addition across unsymmetrical multiple
bond, negative part of the addendum (adding
molecule) gets attached to that carbon atom which
possesses lesser number of hydrogen atoms”.
Mechanism
• Hydrogen bromide provides an electrophile, H+ , which attacks the
double bond to form carbocation as shown below :

• i) The secondary carbocation (b) is more stable than the primary

carbocation (a), therefore, the former predominates because it is formed
at a faster rate
• (ii) The carbocation (b) is attacked by Br– ion to form the product as
follows :
 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 and Hl.
Mechanism : Peroxide effect proceeds via free radical chain mechanism as given
below:
It may be noted that peroxide effect is not observed in the addition
of HCl and HI.

H-Cl bond being stronger than H-Br bond, is not cleaved by the free
radical whereas

H-I bond is weaker and iodine free radicals combine to form iodine
molecules instead of adding to the double bond.
• 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.

• 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.
• Oxidation
a)Hydroxylation
Alkenes react with cold dilute aqueous potassium
permanganate solution
(Baeyer’s reagent) to form 1,2-diols (vicinal) called
glycols. The glycols contain
two –OH groups on adjacent carbon atoms. This reaction
of addition of two
hydroxyl groups to each end of double bond is called
hydroxylation of the double
bond. 2KMnO4+H2O 2KOH+2MnO2+3[O]
• Oxidation

b) Oxidative Cleavage of Alkenes

When alkene is treated with hot acidic potassium
permanganate or potassium
dichromate solution the alkene gets split up at the
double bond forming carboxylic
acids or ketones. This is also called oxidative cleavage of
alkanes.
• Ozonolysis
Alkenes are oxidised with ozone to form ozonides which
are unstable compounds.
These are reduced with zinc and water forming
aldehydes and ketones. The
reaction is called ozonolysis.
• Polymerisation
Polymerisation is a process in which a large number of
simple (same or different) molecules combine to form a
bigger molecule of higher molecular mass. The small
molecule are called monomers while the bigger
molecule are called macromolecules or polymers.
Alkynes
1.14 Alkynes
Alkynes are unsaturated hydrocarbon having carbon-
carbon triple bonds in their molecules. There general
formula is CnH2n-2. The simplest member of this class is
ethyne (C2H2) which is properly known on acetylene.

• C2 H2 H:C:::C:H H—C  C—H

Acetylene
(ethyne)

• C3 H4 CH3CCH Methylacetylene
Propyne
1.15 Structure Of Triple Bond
Ethyne is the simplest molecule of alkyne series. In the
triple bond formation, one sp hybridised orbital of one
carbon atom overlaps axially (head on) with the similar
sp hybrid orbital of the other carbon atom to form σ
bond. Each of the two unhybridised orbitals of one
carbon overlaps sidewise with the similar orbital of the
other carbon atom to form two weak pi bonds. The
remaining sp hybrid of each carbon atom overlaps with
1s orbital of hydrogen to form C-H bond. Thus, carbon
to carbon triple bond is made up of one σ bond and two
pi bonds.
1.16 Nomenclature of
Alkynes
In IUPAC system they are named as derivatives of
corresponding alkanes replacing ‘ane’ by the suffix
‘yne’. The following rules should be followed:
i)The longest continues chain should include both the
carbon atoms of the triple bond.
ii) The suffix used for alkyne is – yne.
iii) The chain is numbered from the end which gives
the lower number to the first carbon atom of the
triple bond.
iv) The positions of the substituents are indicated.
For eg: 4 3 2 1 1 2 3
4 5 6
CH3CH2C≡CH CH3CH2C≡C−CH2CH3
But-1-yne
Hex-3-yne
1.17 Isomerism In
Alkynes
Alkynes exhibit the following structural isomerisms:
Chain Isomerism
The isomers differ in the chain of carbon atoms. For
example, the molecule having molecular formula C5H8
shows chain isomers as:
5 4 3 2 1
CH3−CH2−CH2−C≡CH
Pent-1-yne
Position Isomerism
Alkynes having more than four carbon atoms show
position isomerism. For example:

4 3 2 1
CH3−CH2−C≡CH CH3−C≡C−CH3
1.18 Preparation Of
Alkynes
Preparation Of Alkynes

From calcium carbide From Vicinal Dihalides

i)From Calcium Carbide

Acetylene is prepared in the laboratory as well as an
industrial scale by the action of water on calcium
carbide.
CaC2 + 2H2O HC≡CH + Ca(OH)2
Calcium carbide required for this purpose is obtained by
heating calcium oxide (from limestone) and coke in
an electric furnace at 2275 K.
CaCO3 Heat
CaO + CO2
ii) From Vicinal Dihalides
Vicinal dihalides on treatment with alcoholic
potassium hydroxide undergo
dehydrohalogenation. One molecule of hydrogen
halides is eliminated to form alkenyl halide
which on treatment with sodamide gives alkyne.
1.19 Properties Of Alkynes

1.19.1 Physical Properties

Physical state and smell
The first three members (ethyne, propyne, butyne) of the
family are gases at room temperature, the next eight are
liquid while the higher ones are solid. All alkynes are
colourless. However, ethyne has characteristic odour of
garlic smell.

Solubility
Alkynes are weakly polar in nature. They are lighter than
water and immiscible with water but are soluble in
organic solvents such as petroleum ether, carbon
tetrachloride, benzene, etc.
Melting and Boiling Point
The melting and boiling point of the members of
the family are slightly higher as compared to
those of the corresponding members of alkane
and alkene families. This is due to the fact that
the alkynes have linear structure and therefore,
their molecules are more closely packed in space
as compared to alkanes and alkenes. The
magnitude of attractive forces among them are
higher and therefore,
Hydrocarbo Ethane the Ethene
melting andEthyne
boiling
point are also higher. The melting and boiling
n
point increase with increase in molecular mass
m.p.
of (K)
the alkynes. 101 104 191
b.p. (K) 184.5 171 198
 A. 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

Ethyne is acidic in nature in comparison to ethene and ethane. Justify.

 Ethyne is acidic in nature in comparison to ethene and ethane. Justify

Hydrogen atoms in ethyne are attached to the sp hybridized carbon atoms

Due to the maximum percentage of s-character , the sp hybridized 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 sp3 hybridized orbital of
carbon in 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 atoms are acidic in nature.
 These reactions are not
shown by alkenes
and alkanes, hence
used for distinction
between alkynes,
alkenes and alkanes.

Alkanes, alkenes and alkynes follow the following trend in their

acidic behaviour :
1.19.2 Chemical Properties
Addition of dihydrogen
Alkynes react readily with hydrogen in the presence of
finely divided Ni, Pt or Pd as a catalyst. The reaction is
called hydrogenation.
HC≡CH+H2 Pt/Pd/Ni
[H2C=CH2] H
2
CH3−CH3
Addition of Halogens
Reddish orange colour of the solution of bromine in
carbon tetrachloride is decolourised. This is used as a
test for unsaturation.
Addition of Hydrogen Halides
Two molecule of hydrogen halides(HCl, HBr and HI) add to
alkynes to form gem dihalides (in which two halogens
are attached to the same carbon atom). For example:

Addition of water
Alkenes react with water in the presence of mercuric
sulphate (HgSO4) and sulphuric acid at 333K. The
product are carbonyl compounds (aldehydes and
ketones). For eg:
Polymerisation
a)Linear polymerisation
Linear polymerisation of ethyne takes place to produce
polyacetylene of polythyne which is a high molecular weight
polyene containing repeating units of (CH=CH−CH=CH).

b)Cyclic polymerisation
Alkynes have larger tendency to polymerize then alkenes
and, therefore these give low molecular mass polymers
alkynes when passed through a red hot iron tube at
873k polymerize to give aromatic hydrocarbons. For eg:

This is the best route for entering from aliphatic to

aromatic compounds.
How will you convert ethanoic acid into benzene?
 Aromatic
Hydrocarbon
1.20 Aromatic Hydrocarbon
These hydrocarbons are also known as ‘arenes’. Since most of them
possess pleasant odour (Greek; aroma means pleasant smelling), the class
of compounds was named as ‘aromatic compounds’. The parent member of
the family is benzene having the molecular formula C6H6. it has hexagonal
ring of six carbon atoms with three double bond in alternate position.

Aromatic compounds containing benzene ring are known as benzenoids and

those not containing a benzene ring are known as non-benzenoids. For eg:
1.21 Resonance Structure Of
Benzene
The stability of benzene can be explained on the basis of
concept of resonance. Kekule in1865 gave a ring structure for
benzene in which the positions of the three double bonds are
not fixed. He suggested that the double bond keep on
changing their positions and this is called Resonance. The
resonance structure of benzene is supported by the following
facts:
i)The carbon-carbon bond length in benzene is 139 pm which is
intermediate between bond lengths for C-C bond (154 pm)and C=C
bond (134 pm) and the value is the same for all the bonds.
ii)Due to resonance the pi-electron charge in benzene gets distributed
over greater area i.e., it gets delocalised. As a result of delocalisation
the energy of the resonance hybrid decreases as compared to
contributing structure by about 50kJ mol-1. the decrease in energy is
called resonance energy. Therefore, it is stabilised and behaves as a
saturated hydrocarbon.
iii)If the positions of double bonds are fixed. We expect two
isomers of 1,2-dibromobenzene as shown below (one having
Cl atoms attached to C-C bond and the other having Cl
atoms attached to C=C bond).

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.
 Resonance and Stability of Benzene
• According to the orbital concept, each carbon atom in
benzene is sp2- hybridised and one orbital remains
unhybridised. Out of the three hybrid orbitals, two overlap
axially with the orbitals of the neighbouring carbon atoms on
both side to form σ-bond. The third hybridised orbital of the
carbon atom overlaps with the half-filled orbital of the
hydrogen atom resulting in C-H bonds. Thus, benzene has a
planar structure –with bond angle of120˚ each.
There is still one unhybridised 2p-orbital left on each
carbon atom. Each one of these orbitals can
overlap sidewise with similar orbital of the carbon
atoms on either sides to form three sets of pi-
bonds. (Shown in fig a. and b. respectively)

a) b)
The resultant  -orbital cloud is spread over all the six
carbon atoms (shown in fig c.). As a result, there are two
continuous rings of pi-electron clouds, one above and the
other below the plane of the carbon atoms(shown in fig
d.).

c)
d)

electron cloud
The six π electrons are thus delocalised and can move
freely about the six carbon nuclei, instead of any two.
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.
1.22 Aromaticity
Aromatic compounds are those which resembles benzene in
chemical behaviour. These compounds contain alternate double
and single bonds in a cyclic structure. They undergo substitution
reaction rather than addition reaction. This characteristic
behaviour is called aromaticity. The aromaticity depends upon
the electronic structure of the molecule.

Cyclopentadienyl anion
The main essential for aromaticity are:
Delocalisation: the molecule should contain a cyclic
cloud of delocalized pi electron above and below the
plane of the molecule
Planarity: for the delocalisation of pi-electron the ring
must be planar to allow cyclic overlap of p-orbitals.
Therefore,
𝜋 for a molecule to𝜋be aromatic, the ring must
𝜋
be planar.
(4n+2) electron: for aromaticity, the -electron must
contain a total of (4n+2)
electrons where n is an integer equal to 0,1,2,3……..n .
This is known as Huckel Rule.

Benzene, 6  e- Naphthalene, 10  e- Anthracene,

14  e-
Using the criteria for aromaticity, determine if the following
molecules are aromatic:
1.23 Preparation of
Benzene
 Cyclic polymerisation of ethyne:
 Decarboxylation of aromatic acid
Benzene is prepared in the laboratory by heating sodium benzoate with
soda lime.

 Reduction of phenol
Benzene can be prepared from phenol by distillation with zinc.
1.24 Properties Of
Benzene
1.24.1 Physical Properties

Benzene and its homologues containing up to eight carbon atoms are

colourless liquids with characteristic smell.
Aromatic hydrocarbons are immiscible with water but are soluble in organic
solvents.
They are inflammable and burn with sooty flame.
They are toxic and carcinogenic in nature.
The melting and boiling point of aromatic hydrocarbon increase with
increasing molecular mass. This is due to increase in magnitude of van der
Waals’ forces of attraction with increase in molecular size. Amongst
isomeric arenes, (i.e., o-,m- and p- xylenes), the p- isomer has the highest
melting point because it is most symmetrical.
1.24.2 Chemical
Properties

Chemical
Properties

Mechanism of
Electrophilic
substitution reaction
electrophilic Addition reaction
substitution reaction
Electrophilic Substitution Reaction
i)Nitration
The replacement of a hydrogen atom in the ring by a nitro (-NO 2) group is
called nitration. It is carried out by heating benzene with the nitrating
mixture consisting of conc. nitric acid and conc. sulphuric acid to about
323K-333K.

ii) Halogenation
The replacement of a hydrogen atom in the ring by a halogen atom (F, Cl, Br
or I) is called halogenation. Arenes react with halogen in the presence of a
Lewis acid like anhydrous FeCl3, FeBr3 or AlCl3 to yield haloarenes.
iii)Sulphonation
The replacement of a hydrogen atom in the ring by a sulphonic acid (-SO 3H)
group is called sulphonation. It is carried out by heating benzene with fuming
sulphuric acid (oleum).

iv)Friedel-Crafts Alkylation
When benzene is treated with an alkyl halide in the presence of anhydrous
aluminium chloride, alkylbenzene is formed.
v) Friedel-Crafts Acylation
The reaction of benzene with acyl halide or acid anhydride
in the presence of lewis acid (AlCl3) yields acyl benzene.
If excess of electrophilic reagent is used, further
substitution reaction may take place in which other
hydrogen atoms of benzene 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
chlorinated to hexachlorobenzene (C6Cl6 )
Mechanism of electrophilic
substitution reaction
According to experimental evidences, SE (S= substitution; E=
electrophilic) reaction are supposed to proceed via the following
three steps:
a)Generation of the electrophile.
b)Formation of carbocation intermediate.
c)Removal of proton from the carbocation intermediate.
Step 1: Generation of electrophile
During chlorination, alkylation and acylation of benzene,
anhydrous AlCl3 , being a Lewis acid helps in generation of the
electrophile Cl⊕ , R⊕, RC⊕O (acylium ion) respectively by
combining with the attacking reagent.
In the case of nitration, the electrophile, nitronium ion, NO2+ is
produced by transfer of a proton (from sulphuric acid) to nitric
acid in the following manner:
Step 2:Formation of Carbocation ( arenium ion)
The electrophile E+ approaches the -electron cloud of the aromatic ring and
forms a bond with carbon, creating a positive charge on the ring. This
results in the formation of a sigma complex (called arenium ion).

The arenium ion gets stabilized by resonance

The resulting carbocation has three important contributing structures which

spread the positive charge over the remaining carbon atom.
Step 3: Removal of Proton
The carbocation formed loses a proton to the nucleophile (Nuˉ)
present in the reaction mixture to form a substitution product.
During this step, the aromatic character of the benzene ring is
restored and this step is fast.
The loss of proton allows the two electrons from
the carbon-hydrogen bond to move to regenerate the aromatic
ring and thus restoring the aromatic character.
Addition Reaction
1)Addition of Hydrogen
Benzene reacts with hydrogen in the presence of a catalyst such as nickel, or
platinum at 473 to 573 K under pressure to form cyclohexane.

2) Addition of Halogen
Benzene reacts with chlorine or bromine in the presence of sunlight and
absence of halogen carrier to form benzene hexachloride.

3) Combustion
On completely burning with oxygen, benzene gives carbon dioxide and water
with the evolution of a large amount of energy.

2C6H6 + 15O2  12CO2 + 6H2O +ENERGY

1.25 Directive infl uence of a functional
group in monosubstituted benzene
When monosubstituted benzene is subjected to further
substitution, three possible disubstituted products are not
formed in equal amounts. Two types of behaviour are
observed. Either ortho and para products or meta product is
predominantly formed. 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.
a)Ortho and para directing groups
b)Meta directing group
a) Ortho and para directing
group
The groups which direct the incoming group to ortho and para position
are called ortho and para directing groups. As an example, let us
discuss the directive influence of –OH (phenolic) group.

The resonance structures

of phenol show that the
overall electron density on
the benzene ring increases
in comparison to benzene.
Therefore, it is an activating
group.
b) Meta directing groups
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 an example of Nitro group.

Nitro group reduces the

electron density in the
benzene ring due to its
strong -I effect.
Nitrobenzene is the
resonance hybrid of the
following structures.
1.26 Carcinogenicity and
toxicity
Benzene and polynuclear hydrocarbon
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 reaction and finally damage DNA
and cause cancer.