HYDROCARBONS are the compounds

containing carbon and hydrogen only.

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
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.
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.
 Alkenes : These are hydrocarbon which contain at least one carbon-
carbon bond. For example: Ethene

 Alkynes: These are hydrocarbons which contain at least one carbon-

carbon triple bond. For example: Ethylene
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
Hydrocarbon Characteristic Example
Type Group
CH3CH2CH3
Saturated No double or Triple
Bond Propane
Hydrocarbon:
Alkane
s
Unsaturated
CH3–CH═CH2
Hydrocarbon:
Double Propene
1. Alkenes Bond
CH3−C≡CH
Triple
Bond Propyne
2. Alkynes

Aromatic Benzene
Hydrocarbons: ring
Methyl
Benzene
ALKA
NES
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.
These are simple alkanes without any close chains
and have the general formula where CnH2n + 2 .
Where n is the number of carbon atoms.

For example: i) Methane - CH4

These contain a closed chain or ring in their molecules.
They have the general formula CnH2n.

For example:
i) o
Cyclopropane- r
ii)Cyclobutane o
- r
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˚.
 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)
First of all, select the longest continues chain of carbon atoms in a
molecule.
For CH – CH– CH – CH – CH –CH– CH – CH –
3 2 2 2 2 2

eg: 1 CH3 2 3 4 5 6 7 8 9

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.
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 alkyle
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 9 8 7 6 5 4 3 2 1
eg: CH−CH−CH−CH−CH−CH−CH−CH−CH

CH C−C
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

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
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: CH3CH3

5 4 3 2 1
CH3−CH3−C−CH3−CH3

CH3 CH3

3 -Ethyl-2,3-dimethylpentane
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: 2 3 4 5 6 7 7 6 5 4 3 2
1 1 2−CH−CH2−CH−CH2−CH3
CH3−CH CH3−CH2−CH−CH2−CH−CH2−CH3

CH3 CH2CH3 CH3

CH3CH3

( 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)
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 as 1.the name of such substituents is
given in brackets in order to avoid confusion with the numbering of
the parent chain.
For eg: 1 2 3 4 5 6 7 8 9
CH3−CH3−CH3−CH3−CH3−CH3−CH3−CH3−CH3
1
CH3
2
CH3 Complex Substituent
3
CH3

5-(1,2- Dimenthylpropyl)
Petroleum and natural gas are the main source of
alkanes.
However, alkanes can be prepared by three methods.
Methods for
preparation of
alkanes

From From alkyl From carboxylic

unsaturated
hydrocarbon halides acids
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
tempreture (523-573k) and pressure are required with nickle catalysts.
The hydrogenation reaction of unsaturated hydrocarbon using nickle
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:
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:
 Decarboxylation Kolbe’s electrolytic
reaction method

i) Decarboxylation
reaction : of carboxylic acids on heating with soda lime (mixture
Sodium salts
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

Alkanes are almost non-polar molecules and therefore the molecules are hold
only by weak tfan der Waals forces. The weak intermolecular forces depend
only upon the size and the structure of the molecule. Due to weak forces, the
C1to C4are gases, the next thirteen alkanes from C5to C17are liquid and the
higher member with more than 18 carbon atoms are solid at 298 K.
 Alkanes have generally low boiling points because these are non-polar and
the molecules are held together only by weak tfan der Waals’ forces. With
the increase in the number of carbon atoms, the molecular size
increases and therefore, the magnitude of tfan 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.
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 3 H8 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.
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.

Alkanes are lighter than water. The density increase with the increase in
the number of the carbon atoms.
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.
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:
ii.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.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 chlorine molecule.
ii.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, the one of the product is formed bur free radicals
are consumed and the chain is terminated.
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
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:

i)When a mixture of methane and oxygen in the molar ratio of 9:1 is

compressed to about1100 atmospheres and passed through copper tubes
at 575 K, methane is oxidised to methanol.

2CH4 + O2 Cu/575K/1100 atm.

2CH3OH
ii) When methane is mixed with oxygen and passed through heated
molybdenum oxide (Mo2O3), under pressure it is oxidised to
methanal.
(CH3)3CH + O alk.KMnO4 HCHO +
Alkane isomerise to branched chain alkanes when heated with
anhydrous aluminium chloride (AlCl3) and hydrogen chloride at 573
K under a pressure of about 30-35 atmosphere.
CH3

CH3CH2CH2C anhy.AlCl3,H
Cl
CH3−CH−CH
H3 3

n-butane isopropane
The alkanes containing six or more carbon atoms when heated at about
773K under high pressure of 10-20 atm in the presence of catalyst on
alumina gel get converted to aromatic compounds. This process is
called aromatization.

CH3− 773K, 10-20

atm
(CH2)4−CH3 Benzen
On passing a mixture of steam and methane over heated nickle
(supported over alumina, Al2O3) catalyst at 1273 K, methane is
oxidised to carbon monoxide and hydrogen is evolved.
CH4 +H2O CO + 3H2

When higher alkanes are heated to high tempreture in the presence of

alumina or silica catalysts, the alkanes break down to lower alkanes
and alkenes. For eg:
C3H8 C2H4 + CH4 or C3H6 + H2
This reaction is called Fragmentation or Cracking or Pyrolysis. Pyrolysis
of hexane gives following product:
Chemist represent conformations in two simple ways:
a)Sawhorse representation b)Newman projection

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
there are carbon is shown as the upper right hand carbon.
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.
Alkene
s
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.

Propylene
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 bondcompounds by
combining with the electrophilic
reagents.
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 CH3CH=CHCHCH3 CH2=CH−CH=CH2
eg: CH3
4-Methylpent-2-ene Buta-1,3-diene
 Isomerism in Alkanes

Structural Isomerism Geometrical Isomerism

Chain Position
Isomerism Isomerism
Alkenes show following types of structural isomerisms:

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:

The isomers differ in the position of the double

bonds. For eg:
The compounds which have the same structural formula but differ in the
spatial arrangement of atoms or groups of atoms about the double
bond are called geometrical isomers and the phenomena is known as
geometrical isomerism. The isomers in which similar atoms or groups lie
on the same side of the double bond is called cis-isomers while the
other in which they are displaced on opposite sides, is called trans-
isomerism.

Cis-isomer is more polar than trans-isomers. These are distinguish on the

basis of their physical properties such as melting point, boiling point
etc.
 From
Al k yn e s

From Alkyl
Halides
Pre p arat i o n
Of Al kane s
From Vicinal
Dihalides

From
Al co h o l s
Alkynes can be reduced to alkenes using palladium charcoal
(palladised charcoal) catalyst partially deactivated with poison like
sulphur compounds or quioline. 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).

For CH3−C≡C−CH3 Pd- C, H2 CH3CH═CHCH3

eg: But-2-yne But-2-ene
CH3–C≡CH+H2 CH3–CH=CH2
Propyne Propene
Pd/C
CH≡CH+H2 CH2=CH2
Ethyne Ethene
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>
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 CH3CHBr−CH2Br+Zn CH3CH=CH2+ZnBr
eg:

Alkenes are prepared from alcohols by heating with protonic acids such
as sulphuric acid at about 443K. This reaction is called dehydration
of alcohols.
For CH3CH2OH H2SO4 or H3PO4 CH2=CH2+H2O
eg: reaction is also an example of β-elimination reaction because –OH
This
group takes out one hydrogen atom from the β- carbon atom.
In general, alkenes have higher melting point than the corresponding alkanes.
This is due to the reason that p-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.

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˚.
Alkenes are weakly polar. The p-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.

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.
Alkenes add up on molecule of dihydrogen gas in the presence
of finally divided nickle, palladium or platinum to form
alkanes.

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.

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
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,
the negative part of the
addendum (attacking
molecule)joins with the
carbon atom which carries
smaller number of hydrogen
atoms while the positive part
goes to the carbon atom with
more hydrogen atom.”
Cold concentrated sulphuric acid adds to alkenes in accordance with
Markovnikov rule to form alkyl hydrogen sulphate by the
electrophilic addition reaction.

In the presence of a few drops of concentrated sulphuric acid alkenes

react with water to form alcohols, in accordance with the
Markovnikov rule.
Alkenes react with cold dilute aqueous or alkaline potassium
permanganate solution to form 1,2-diols 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.
For 2KMnO4+H2O 2KOH+2MnO2+3[O]
eg:

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.
For CH3−CH=CH−CH3 KMnO /H+
4 2CH3COOH
eg: But-2-ene Ethanoic acid
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 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.
Alkyne
s
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.
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.
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 34 5 6
CH3CH2C≡CH
CH3CH2C≡C−CH2CH3
But-1-yne Hex-3-
yne
Alkynes exhibit the following structural
isomerisms:

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

Alkynes having more than four carbon atoms show position isomerism.
For 4 3 2 1 4 3 2 1
example: CH3−CH2−C≡CH CH3−C≡C−CH3
But-1-yne But-2-yne
 Preparation Of
Alkynes

From calcium carbide From Vicinal Dihalides

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

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.
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, the melting
and boiling point are also higher. The melting and boiling point
increase with increase in molecular mass of the alkynes.

Hydrocarbon Ethane Ethene Ethyne

m.p. (K) 101 104 191

b.p. (K) 184.5 171 198

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] H2

CH3−CH3

Reddish orange colour of the solution of bromine in carbon tetrachloride

is decolourised. This is used as a test for unsaturation.
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:

Alkenes react with water in the presence of mercuric sulphate (HgSO4)

and sulphuric acid at 337K. The product are carbonyl compounds
(aldehydes and ketones).
For eg:
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).

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.
 Aromatic
Hydrocarbo
n
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:
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 an 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- dichlorobenzene as shown below (one having Cl atoms attached to
C-C bond and the other having Cl atoms attached to C=C bond).
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 two sets of pi-bonds. (Shown in fig a. and b. respectively)
a) b)
The resultant pi-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
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 be behaviour is called
aromaticity. The aromaticity depends upon the electronic structure of
the molecule.

Cyclopentadienyl
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, for a molecule
to be aromatic, the ring must be planar.
 (4n+2) pi-electron: for aromaticity, the pi-electron could must contain
a total of (4n+2)pi electrons where n is an integer equal to
0,1,2,3……..n
. This is known as Huckel Rule.

Benzene, 6 pi e- Naphthalene, 10 pi e- Anthracene, 14 pi

e-
 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.
 Benzene and its 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.
 Chemical
Properties

Mechanism of
Electrophilic
electrophilic Addition reaction
substitution reaction
substitution reaction
The replacement of a hydrogen atom in the ring by a nitro (-NO2) group is
called nitration. It is carried out by heating benzene with the nitrating
mixture consisting of concentrated nitric acid and sulphuric acid to
about 330K.

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.
 The replacement of a hydrogen atom in the ring by a sulphonic acid (-SO3H)
group is called sulphonation.
It is carried out by heating
benzene with fuming
sulphuric acid and oleum.

When benzene is treated with an alkyl halide in the presence of

anhydrous aluminium chloride, alkylbenene is formed.

The reaction of benzene with acyl halide

or acid anhydride in the presence of
lewis acid (AlCl3) Yields acyl benzene
According to experimental evidences, SE (S= substitution; E= electrophilic)
a)Generation ofsupposed
reaction are the electrophile.
to proceed via the following three steps:
b)Formation of carbocation
intermediate.
c)Removal of proton from the
carbonation intermediate.

The attacking reagent may not be strong electrophile.

Therefore, first of all an electrophile is generated by some
preliminary reaction. For example , during chlorination of
benzene, an electrophile (Cl +) is generated by reacting
with anhydrous AlCl3 used as catalyst.
The electrophile E+ approaches the pi-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.
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.
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.

Benzene reacts with chlorine or bromine in the presence of sunlight

and absence of halogen carrier to form benzene hexachloride.
On completely burning with oxygen, benzene gives carbon
dioxide and water with the evolution of a large amount
of energy.
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
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
 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.
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.