HYDROCARBONS

Classification
Depending upon the types of carbon-carbon bonds present, hydrocarbons
can be classified into three main categories
Saturated Hydrocarbons
Unsaturated Hydrocarbons
Aromatic Hydrocarbons
Saturated hydrocarbons contain carbon-carbon and carbon-hydrogen
single bonds.
If carbon atoms form a closed chain or a ring, they are termed as
cycloalkanes. Aromatic hydrocarbons are a special type of cyclic
compounds
Unsaturated hydrocarbons contain carbon-carbon multiple bonds –
double bonds, triple bonds or both.
 ALKANES
Hydrocarbons have adjacent carbon atoms with single bond
General formula for Alkanes is CnH2n+2
 Nomenclature and Isomerism
Methane, Ethane and Propane have only one structure but higher
alkanes have more than one structure
Consider structure of Butane C4H10

Butane (n- butane) 2-Methylpropane (isobutane)

These two structures have same molecular formula which are known
as Structural Isomers
Isomers of pentane

2,2-Dimethylpropane (neopentane)

Structural isomers which differ in chain of carbon atoms are known as

Chain Isomers
 Preparation
From Unsaturated Hydrocarbons

Dihydrogen is added to alkenes and alkynes in the presence of finely

divided catalysts like platinum, palladium or nickel to form alkanes.
This process is called Hydrogenation.
From Alkyl Halides
Alkyl halides on reduction with zinc and dilute hydrochloric acid
give alkane
• Except fluorides, all halides are used.

Wurtz reaction: Alkyl halides on treatment with sodium metal in

presence of dry ether solution give higher alkanes.
From carboxylic acids

Decarboxylation: The process of elimination of carbon dioxide from a

carboxylic acid

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

salt of a carboxylic acid on electrolysis gives alkane.
1. At ANODE: 2CH3COO- CH3CH3 +2CO2 +2e-
2. At CATHODE: H2O H+
: 2H+ +2e- H2

Electrolysis
Physical properties

Alkanes are non-polar molecules.

They are colourless and odourless.
They possess weak van der Waals forces.
Boiling point (b.p.) of alkanes increase with increase in molecular
mass.
Alkanes can be separated by distillation. They are produced in
industry by fractional distillation of petroleum and natural gas
Chemical properties
Substitution reactions:
Halogenation: The replacement of one or more hydrogen atoms in an
organic compound by a halogens, nitro group and sulphonic acid group.
In this a C-H bond is broken and a new C-X bond is formed

Light

CH4 (g)+ Cl2 (g)  CH 3Cl (g) + HCl (g)

chloromethane
Light

CH3Cl (g) + Cl2 (g)  dichloromethane

CH2Cl2 (g) + HCl (g)
Light

CH2Cl2 (g) + Cl2 (g)  CHCl 3 (g) + HCl (g)

trichloromethane
Light

Tetrechloromethane
CHCl3 (g) + Cl2 (g)  CCl (g)+ HCl (g)
Carbon4tetrachloride
Halogenation is proceeded via free radical chain mechanism involving
three steps
Initiation: Formation of radicals
Cl2  Cl• + Cl•

Propagation: Radicals attack substrates making new molecules and new

radicals

CH4(g) + Cl•(g)  CH3• (g) + HCl (g)

CH3 •(g) + Cl•(g)  CH3Cl(g)

Termination: Radical recombines with another and the reaction is

terminated. Cl• (g) + Cl• (g)  Cl2 (g)

H3C• + CH3•  H3C - CH3

H3C• + Cl•  H3C - Cl

Combustion:
At high temperatures alkanes combust

CH4(g) + 2O2(g)  CO2(g) + 2H2O(g) ΔHo = -890.4 kJ

C2H6(g) + 7O2(g)  4CO2(g) + 6 H2O(g) ΔHo = -3119 kJ

The reactions are all highly exothermic.
The general combustion equation for any alkane is

Incomplete Combustion:
CH4 (g) + O2 (g)  C (s) + 2H2O(l)
Carbon black
Controlled oxidation
Alkanes on heating with air at high pressure and in presence of
catalyst gives oxidation products
Cu/523K
2CH4 + O2 
100atm 2CH3OH
Methanol
Mo2O3

CH4 + O2 
Δ HCHO
Methanal + H2O
(CH3COOH)2 Mn

2CH3CH3 + 3O2 Δ
 2CH 3COOH + 2H2O
Ethanoic acid

Alkanes having tertiary H atom can be oxidized to corresponding

alcohols by potassium permanganate
KMnO4
(CH3)3CH  (CH3)3COH
2-Methylpropane 2-Methylpropan-2-ol
 Isomerisation
n-Alkanes on heating in the presence of anhydrous aluminium chloride
and hydrogen chloride gas isomerizes to branched chain alkanes

Anhy. AlCl3/HCl

Aromatization
Alkanes having six or more carbon atoms on heating in the presence of
oxides of vanadium , molybdenum or chromium get dehydrogenated and
cyclised to benzene
 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
Ni
CH4 + CO + 3H2
Δ
Pyrolysis
Higher alkanes on heating to higher temperature decompose into lower
alkanes, alkenes etc. Such a decomposition reaction is called Pyrolysis.
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

Eclipsed Conformation: In this conformation the hydrogen atoms

attached to carbons are as closed together as possible
Staggered Conformation: In this conformation the hydrogen atoms
attached to carbons are as far apart as possible
Sawhorse Projections

Newman Projections
 Alkenes
Alkenes are unsaturated hydrocarbons containing at least one double
bond.
Alkenes have general molecular formula CnH2n
Structure of Double Bond
Carbon-carbon double bond in alkenes consists of one strong sigma ( σ)
bond and one weak pi (π) bond.
Nomenclature
Identify the longest chain containing both C of the double bond.
Replace –ane to –ene.
The longest chain is numbered from the end nearest to the double
bond.
The compound having two double bonds ends in –adiene.
A cyclic compound is named as cycloalkene.
Numbering in cycloalkene starts from the carbon containing double
bond.
 Isomerism
Structural Isomerism
Position Isomers
Geometrical isomerism

Geometric isomers are possible only when each carbon of the double
bond is a stereocenters.
Cis Isomer: Two identical atoms or groups lie on the same side of
the double bond.
Trans Isomer: Identical atoms or groups lie on the opposite sides of
the double bond
 Preparation
From alkynes
Alkynes on partial reduction with calculated amount of dihydrogen
in the presence of palladised charcoal partially deactivated with
poisons like sulphur compounds or quinoline give alkenes.
Partially deactivated palletized charcoal is known as Lindlar’s
Catalyst
Alkynes on reduction with sodium in liquid ammonia form trans alkenes.
From alkyl halides
Dehydrohalogenation: Alkyl halides (R-X) on heating with alcoholic
potash eliminate one molecule of halogen acid to form alkenes. This
reaction is known as dehydrohalogenation
The removal of halogen acid.
Hydrogen atom is eliminated from the β carbon atom it is β-
elimination reaction.
From Vicinal Dihalides

Dihalides in which two halogen atoms are attached to two adjacent

carbon atoms are known as Vicinal Dihalides

From alcohols by acidic dehydration

A water molecule is eliminated from the alcohol molecule in the
presence of an acid, this reaction is known as acidic dehydration of
alcohols
Physical properties

Alkenes are non polar compounds.

They are insoluble in water and soluble in non polar organic solvents.

They are less dense than water.

The alkenes has a boiling point which is a lower than the corresponding
alkanes.

Straight chain alkenes have higher boiling point than isomeric

branched chain compounds.
Chemical properties
Addition of dihydrogen:
Alkenes add up one molecule of dihydrogen gas to form alkanes

Addition of halogens :
Halogens react with alkene to form vicinal dihalides.
Addition of hydrogen halides:
Hydrogen halides (HCl, HBr,HI) add up to alkenes to form alkyl halides

Markovnikov Rule: (Addition reaction of HBr to unsymmetrical alkenes)

Markovnikov's rule states that the hydrogen atom adds to the carbon
atom that already has the larger number of hydrogen atoms when HX
adds to an alkene.
 Anti-Markovnikff’s 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.
Addition of sulphuric acid:
Cold concentrated sulphuric acid adds to alkenes 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

Oxidation:
Alkenes on reaction with cold, dilute, aqueous solution of potassium
permanganate produce vicinal glycols
Acidic potassium permanganate or acidic potassium dichromate
oxidises alkenes to ketones and/or acids depending upon the nature
of the alkene
Ozonolysis:
Ozonolysis of alkenes involves the addition of ozone molecule to
alkene to form ozonide.
This reaction is highly useful in detecting the position of the double
bond in alkenes

Zn+H2O
Polymerisation:
Polythene is obtained by the combination of large number of ethene
molecules at high temperature, high pressurein the presence of a
catalyst. This reaction is known as polymerisation.
The simple compounds from which polymers are made are called
monomers.
 Alkynes
Hydrocarbons have adjacent carbon atoms with triple bonds are
alkynes.
Alkynes have general molecular formula CnH 2n – 2.
The first stable member of alkyne series is ethyne which is
popularly known as acetylene.
 Nomenclature and Isomerism
In IUPAC alkynes are named as derivatives of the corresponding
alkanes replacing ‘ane’ by the suffix ‘yne’.
Structures I and II are position isomers and structures I and III or
II and III are chain isomers.
Structure of Triple Bond
The carbon atom of ethyne has two sp hybridised orbitals.
Ethyne molecule consists of one C–C σ bond, two C–H σ bonds and
two C–C π bonds
 Preparation
From Calcium Carbide
Ethyne is prepared by treating calcium carbide with water
From Vicinal Dihalides

Vicinal dihalides on treatment with alcoholic potassium hydroxide

undergo Dehydrohalogenation
Physical properties

First three members are gases, the next eight are liquids and the higher
ones are solids.
All alkynes are colourless.
Ethyne has characteristic odour. Other members are odourless.
Alkynes are weakly polar in nature.
They are lighter than water and immiscible with water but soluble in
organic solvents like ethers, carbon tetrachloride and benzene
Chemical properties
Acidic character of alkyne:
Sodium metal react with ethyne to form sodium acetylide with the
liberation of dihydrogen gas
Ethyne is acidic in nature in comparison to ethene and ethane since
the hydrogen atoms of ethyne which are attached to triply bonded
carbon atom are acidic in nature.
Addition reactions:
Addition of dihydrogen
 Addition of halogens

Reddish orange colour of the solution of bromine in carbon tetrachloride

is decolourised.

Addition of hydrogen halides

 Addition of water

Addition of water to alkynes on warming with mercuric sulphate and

dilute sulphuric acid at 333 K forms carbonyl compounds
Polymerisation
Linear polymerisation:

Linear polymerisation of ethyne takes place to produce

polyacetylene or polyethyne.
—( CH = CH – CH = CH)n—
Thin film of polyacetylene can be used as electrodes in batteries.
These films are good conductors, lighter and cheaper than the
metal conductors.
Cyclic polymerisation:
Ethyne on passing through red hot iron tube at 873K undergoes
cyclic polymerization.
Three molecules of ethyne polymerise to form benzene.

b
 Aromatic Hydrocarbon
Aromatic hydrocarbons are also known as Arenes
Benzenoids: Aromatic compounds which contains benzene ring
Non-benzenoids: Aromatic compounds which does not contains a
benzene ring.

Examples of Arenes
Nomenclature and Isomerism

Aromatic compounds are named with benzene as the parent chain.

One side group is named in front of the name benzene.
No number is needed for mono-substituted benzene since all the
ring positions are identical

Methylbenzene Chlorobenzene
(toluene)
When two groups are attached to benzene, the ring is numbered to
give the lower numbers to the side groups

Some substituted benzene rings also use a common name. Then naming
with additional more side groups uses the ortho-, meta-, para- system.
Structure of Benzene
Benzene is a flat, symmetrical molecule
It’s molecular formula C6H6
It has alternating three carbon-carbon double and three single bonds
Benzene’s relatively lack of chemical reactivity is due to its structure.
There are two possible structures with alternating double and single
bonds
Resonance and stability of benzene
The hybrid structure is represented by inserting a circle or a dotted
circle in the hexagon

All the six carbon atoms in benzene are hybridized.

Each carbon atom is now left with one unhybridisedp orbital perpendicular
to the plane of the ring.
 The unhybridised p orbital of carbon atoms form a π bond by lateral
overlap.

Presence of delocalised π electrons in benzene makes it more stable

than the hypothetical cyclohexatriene.
Aromaticity

Hückel Rule: Characteristics

Planarity
Complete delocalisation of the π electrons in the ring
Presence of (4n+ 2) π electrons in the ring where nis an integer (n=
0, 1, 2, . . .)
 Preparation of Benzene
Cyclic polymerization of ethyne

Three molecules of ethyne polymerize to form benzene

 Decarboxylation of aromatic acids

Sodium salt of benzoic acid on heating with sodalime gives benzene.

Reduction of phenol
By passing Phenol vapours over heated zinc dust, benzene is formed
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.
 Chemical properties
Arenes are characterised by electrophilic substitution reactions

Electrophilic substitution reactions

Nitration:
A nitro group is introduced into benzene ring when benzene is heated with a
mixture of concentrated nitric acid and concentrated sulphuric acid

323 -333K
Halogenation:

Arenes react with halogens in the presence of a Lewis acid to yield

haloarenes.
Sulphonation:

The replacement of a hydrogen atom by a sulphonic acid group in a

ring is called sulphonation
Friedel-Crafts alkylation reaction:

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

anhydrous aluminium chloride, alkylbenene is formed.
Friedel-Crafts acylation reaction:
The reaction of benzene with an acyl halide or acid anhydride in the
presence of Lewis acids yields acyl benzene.
If excess of electrophilic reagent is used, further substitution reaction
takes place.
 Mechanism of Electrophilic Substitution Reactions

Three steps involved in reactions are:

• Generation of the eletrophile
• Formation of carbocation intermediate
• Removal of proton from the carbocation intermediate
 Generation of Electrophile E⊕
During chlorination, alkylation and acylation of benzene, anhydrous ,
being a Lewis acid helps in generation of the electrophile , ,(acylium ion)
respectively by combining with the attacking reagent.
The electrophile, nitroniumion, is produced by transfer of a proton
(from sulphuric acid) to nitric acid.
In this process ,sulphuric acid serves as an acid and nitric acid as a
base.
 Formation of Carbocation(arenium ion)
Attack of electrophile results in the formation of σ-complex or areniumion
in which one of the carbon is hybridised.

The arenium ion gets stabilised by resonance

Removal of proton:
Sigma complex or arenium ion loses its aromatic character because
delocalisation of electrons stops at hybridised carbon.
To restore the aromatic character, σ-complex releases proton from sp3
hybridised carbon on attack by [AlCl4]–and [HSO4]–
Addition reactions
At high temperature and/ or pressure in the presence of nickel
catalyst, Hydrogenation of benzene gives cyclohexane.

Under utra-violet light, three chlorine molecules add to benzene to

produce Benzene hexachloridecalled gammaxane()
 Combustion:
When heated in air, benzene burns with sooty flame producing and

General combustion reaction for any hydrocarbon is:

 Directive influence of a functional group in
Monosubstituted Benzene

When mono substituted benzene is subjected to further substitution

either ortho and para products or meta product are predominantly
formed .
This 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
Ortho and para directing groups:
The groups which direct the incoming group to ortho and para positions
are called ortho and para directing groups.

The electron density is more on o – and p – positions. Hence, the

substitution takes place mainly at these positions.
–OH group activates the benzene ring for the attack by an electrophile.
Meta directing group:
The groups which direct the incoming group to meta position are
called meta directing groups.

The overall electron density on

benzene ring decreases
making further substitution
difficult, these are also called
‘deactivating groups’.

The electron density on o– and p– position is comparatively less than

that at meta position. Hence the electrophile attacks on meta position
 Carcinogenicity And Toxicity
Benzene and polynuclear hydrocarbons containing more than two
benzene rings merged together are toxic and possess carcinogenic
property.
They enter into human body and undergo biochemical reactions
which damage DNA and cause cancer.

Eg: