Molecules which do not

contain benzene rings are

referred to aliphatic
("fat-like") compounds.

The aromatic
hydrocarbons contain
The aromatic hydrocarbons contain ring
ring systems
systems with electron
with a delocalized a
delocalized electron
clouds
clouds (pi bonds in alternative
positions)
Examples of aliphatic heterocyclic compounds
C-C and C-H bond lengths are 154 pm and 112 pm respectively
4-Ethyl-2,3-dimethyl heptane
Pi bond
Since difference in properties is due to difference in
their structures, they are known as structural isomers
Such structural isomers which differ in chain of carbon
atoms are known as chain isomers
Preparation of alkanes
1.From unsaturated hydrocarbons
Dihydrogen gas adds to alkenes and alkynes in the
presence of finely divided catalysts like platinum,
palladium or nickel to form alkanes.
This process is called hydrogenation
2.From alkyl halides
Alkyl halides (except fluorides) on reduction
with zinc and dilute hydrochloric acid give alkanes
Wurtz reaction
Alkyl halides on treatment with sodium metal in dry
ethereal (free from moisture) solution give higher alkanes
It is used for the preparation of higher alkanes containing
even number of carbon atoms
Diethyl ether(C2H5)2O that is completely devoid of water is known as dry ether(NON POLAR)
3. From carboxylic acids
Sodium salts of carboxylic acids on heating with soda lime
(mixture of sodium hydroxide and calcium oxide) give
alkanes containing one carbon atom less than the
carboxylic acid.
This process of elimination of carbon dioxide from a
carboxylic acid is known as decarboxylation
Kolbe’s electrolytic method
Sodium or Potassium salt of a carboxylic acid on electrolysis gives alkane
Physical Properties of Alkanes
1. Structures of Alkanes
sp3 hybridised ,General configuration of alkane is CnH2n+2. They exhibit tetrahedral
geometry with a bond angle of 109.47° between them.
2.Solubility of Alkanes
alkanes are generally non-polar molecules,Alkanes are hydrophobic in nature, alkanes are
insoluble in water, they are soluble in organic solvents.
3.Boiling Point of Alkanes
As the intermolecular Van Der Waals forces increase with the increase of the molecular size or
the surface area of the molecule we observe,
The boiling point of alkanes increases with increasing molecular weight.
The straight-chain alkanes are observed to have a higher boiling point in comparison to their
structural isomers.
4.Melting Point of Alkanes
The melting point of alkanes follows the same trend as their boiling point, that is, it increases
with an increase in molecular weight
Chemical properties
1.Substitution reactions
Halogenation takes place either at higher temperature (573-773 K)
or in the presence of diffused sunlight or ultraviolet light. These
reactions in which hydrogen atoms of alkanes are substituted are
known as substitution reactions.
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
During incomplete combustion of alkanes with insufficient amount of air or
dioxygen, carbon black
used in the manufacture of ink, printer ink, black pigments and as filters
Pyrolysis
Higher alkanes on heating to higher temperature decompose into, alkenes or lower alkanes etc.
Such a decomposition reaction into smaller fragments by the application of heat is called
pyrolysis or cracking

Preparation of oil gas or petrol gas from kerosene oil or petrol involves the
principle of pyrolysis
Conformations
Such 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.

Conformations of ethane – YouTube

This rotation results into infinite number of spatial arrangements of

hydrogen atoms attached to one carbon atom with respect to the
hydrogen atoms attached to the other carbon atom. These are called
conformational isomers (conformers).
Eclipsed and the staggered conformations can be represented
by Sawhorse and Newman projections( 2D view)
Sawhorse projections Newman projections
side-on appearance of a molecule angular appearance of a molecule
 Newman projections

hydrogen atoms attached to two carbons

are as closed together as possible hydrogens are as far apart as possible is
is called eclipsed conformation known as the staggered conformation
The staggered conformers are more stable than the eclipsed conformers
The repulsive interaction between the electron clouds, which affects stability
of a conformation, is called torsional strain.
Angle of rotation about C–C bond. This angle is also called dihedral angle or
torsional angle
2
Octa-1,3,5,7-tetraene
OR
1,3,5,7 Octatetraene
Alkenes
 Geometrical isomerism-Cis and trans isomer

Stereoisomers of this type are called geometrical isomers.

The isomer of the type (a), in which two identical atoms or groups lie on the same side of the double
bond is called cis isomer

type(b), in which identical

atoms or groups lie on the opposite sides of the double
bond is called trans isomer .
Thus cis and trans isomers have the same structure but have different configuration (arrangement of atoms or
groups in space).Hence properties are also different.
Preparation of alkene
1.Alkynes on partial reduction with calculated amount of dihydrogen in the presence of
palladised charcoal
Partially deactivated palladised charcoal is known as Lindlar’s catalyst.
Charcoal is deactiviated
with Sulphur or quinoline
2.From alkyl halides:-
called as dehydrohalogenation(removal of halogen acid)
β-elimination reaction(since hydrogen atom is eliminated from the β carbon
atom)

iodine > bromine > chlorine

3.From vicinal dihalides: Vicinal halide reacts with Zn
This reaction is known as dehalogenation
Dihalides in which two halogen atoms are attached to two adjacent
carbon atoms are known as vicinal dihalides
4.From alcohols by acidic dehydration:
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 of alkenes
 C1-C3/C4 are gases,
 C5-C8 are liquids and
 the higher ones are solids.
 Ethene is a colourless gas with a faint sweet smell.
 All other alkenes are colourless and odourless,
 insoluble in water
 fairly soluble in non-polar solvents like benzene, petroleum, ether etc.
 They show a regular increase in boiling point with increase in size
Nonpolar solvents include
Alkanes (pentane, hexane, heptane etc)
Aromatics (benzene, toluene, and xylene)
small difference in the
electronegativity of
C and H, their bond is
symmetrical molecule in which all the regarded as nonpolar.
bond dipoles cancel.
Chemical Properties
 Addition of dihydrogen

 Addition of halogens

CCl4 is used since it helps to dissolve the reactants in the

process as it contains no protons
Addition of hydrogen halides:
HI > HBr > HCl

Addition reaction of HBr to symmetrical alkenes-(similar groups attached to

double bond)
 MARKOVNIKOV RULE & ANTI MARKOVNIKOV RULE
Addition reaction of HBr to unsymmetrical alkenes(dissimilarity in the groups attached to
double bond)

addendum
Markovnikov rule
The rule states that negative part of the addendum (adding molecule) gets
attached to that carbon atom which possesses lesser number of hydrogen
atoms.
 Markovnikov rule
The rule states that negative part of
the addendum (adding molecule) gets
attached to that carbon atom which
possesses lesser number of hydrogen
atoms.

Anti markovnikov rule

Negative part of the addendum
Anti Markovnikov addition or peroxide effect or Kharash effect is added to the carbon with
more number of hydrogen
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:
Alkenes on reaction with cold, dilute, aqueous solution of potassium
permanganate (Baeyer’s reagent) produce vicinal glycols.
Decolorisation of KMnO4 solution is used as a test for unsaturation
Ozonolysis :
Ozonolysis of alkenes involves the addition of ozone molecule to alkene
to form ozonide, and then cleavage of the ozonide by Zn-H2O to smaller
molecules.
ALKYNES
Preparation of Alkynes
1. From calcium carbide
2.From vicinal dihalides

ethyne

sodamide
Physical Properties
 C1,C2 and C3 are gases,
 C4 TO C11 are liquids
 Above C11 higher ones are solids.
 alkynes are colourless.
 Ethyene has characteristic odour.
 Other members are odourless.
 Alkynes are weakly polar in nature.
 They are lighter than water and immiscible with water
 soluble in organic solvents like ethers, carbon tetrachloride
and benzene.
 Their melting point, boiling point and density increase with
increase in molar mass
Acidic character of alkyne:

 Sodamide(NaNH2) is used
 Sodaamide reacts with propyne to form sodium propynide with the
liberation of dihydrogen gas
Addition reactions
Addition of dihydrogen

Addition of halogen
Addition of hydrogen halides

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

Like alkanes and alkenes, alkynes are also immiscible and do not react with
water.
One molecule of water adds to alkynes on warming with mercuric sulphate
and dilute sulphuric acid at 333 K to form carbonyl compounds
AROMATIC HYDROCARBON
These hydrocarbons are also known as ‘arenes’.
Since most of them possess pleasant odour
(Greek; aroma meaning pleasant smelling)
Structure of Benzene
Benzene was isolated & described benzene by Michael Faraday

August Kekule-visualized the ring structure of benzene

Preparation of benzene

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

Removes oxygen from benzene

derivative
Physical properties OF AROMATIC COMPOUNDS
 Non- polar
 Colourless solid or liquid except very few
 Usage-cosmetics, detergent, dyestuff, food, fuel,
petrochemicals, pharmaceuticals, plastics, and
rubber,naphthalene balls
 Aromatic hydrocarbons are immiscible with water
 Miscible with non -polar organic solvents (CCl4,kerosene etc)
 burn with sooty flame
Electrophilic substitution reactions

The common electrophilic substitution reactions of arenes are

 Nitration-presence of con H2SO4 /Con HN03
 Halogenation- presence of anhydrous AlCl3/FeBr3/FeBr3
 Sulphonation-fuming sulphuric acid
H2S2O7(H2SO4+SO3) - Fuming Sulphuric acid is also known as oleum
Fuming sulphuric acid is an inorganic acid, that can be produced by the
addition of sulfur trioxide to concentrated sulphuric acid
 Friedel Craft’s alkylation and acylation reactions in which attacking
reagent is an electrophile (E+ )
Nitration

concentrated nitric acid and

concentrated sulphuric acid
Halogenation
Arenes react in the presence of anhydrous AlCl3 to yield haloarenes.
iii) Sulphonation

H2S2O7(H2SO4+SO3) - Fuming Sulphuric acid is also known as oleum

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

Acyl halide - Acetyl chloride

Acid anhydride - Acetic anhydride
Directive influence of a functional group in monosubstituted benzene

Ortho and para directing groups: activating groups

Electron density is more in 0- and P- positions than M
Meta directing group-deactivating groups
Electron density around O- and P- are less than that of M- position
CARCINOGENICITY AND TOXICITY

 Benzene and polynuclear hydrocarbons containing more than two

benzene rings fused together are toxic and said to possess cancer
producing (carcinogenic) property
 polynuclear hydrocarbons are formed on incomplete combustion of
organic materials like tobacco, coal and petroleum.
 damage DNA and cause cancer