Preparations/Synthesis and

Reactions of Alkanes
Petroleum and natural gas are the main source of
alkanes. However, alkanes can be prepared by
different methods.
a) Decarboxylation
b) Wurtz Synthesis
c) Hydrolysis of Grignard Reagent
d) Reduction of Alkyl Halide
a) Decarboxylation
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.
The process of elimination of carbon dioxide from a
carboxylic acid is known as decarboxylation.
a) Decarboxylation
Replacement of the carbonyl group by a hydrogen.
Method used in the laboratory preparation of methane gas.
Uses soda lime as decarboxylating agent ( NaOH and CaO).
b) Wurtz Synthesis
 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.

CHARLES ADOLPHE WURTZ

b) Wurtz Synthesis
reaction between metallic Na and two alkyl halides , R-X, in the
presence of dry ether
c) Hydrolysis of Grignard Reagent
Grignard Reagent is an organo metallic compound in which the C is
bonded to a metal, with a general formula of R-Mg-X (alkyl magnesium
halide).
d) Reduction of Alkyl Halide
involves the replacement of the halogen atom by a hydrogen
atom.
it can be obtained by the action of HCl in Zn, alcohol in Na, H 2
in Pt or Pd
d) Reduction of Alkyl Halide
Alkyl halides (except fluorides) on reduction with zinc and
dilute hydrochloric acid give alkanes.
Reaction of Alkanes
Reaction of Alkanes
Very few chemicals react with alkanes, this is why they are nicknamed
“the paraffins” meaning little affinity or little reactivity.
a) Combustion
b) Halogenation
c) Nitration
d) Cracking or Pyrolysis
e) Isomerization
a) Combustion
burning of gas, liquid or solid in which the fuel is oxidized, evolving heat
and often light.
Alkanes react with air or oxygen to produce carbon dioxide, water, and
energy.
a) 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
E.g.

The general combustion equation for any alkane is:

Due to the evolution of large amount of heat during combustion, alkanes are used
as fuels cells.
b) 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˚.
Mechanism of halogenation reaction
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.
Mechanism of halogenation reaction
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.
Mechanism of halogenation reaction
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 but free radicals are
consumed and the chain is terminated.
b) Halogenation
Alkanes react with halogens (F₂, Cl₂, Br₂, or I₂) by process called
substitution in which a halogen atom substitutes for a hydrogen atom.
This type of reaction is called halogenation, and the products are
haloalkanes (alkyl halides).
c) Nitration
Alkanes react with HNO3 at an elevated temperature of 450oC. The
process is called vapor phase nitration and yields a class of compounds
called nitro alkanes.
d) Cracking or Pyrolysis
is the decomposition of the compound by the action of heat alone.
an alkane is passed through a hot metal tube at 500-700 oC. The C-C
and C-H bonds are cleaved and the alkane breaks down into a mixture of
lower mol. wt. alkanes, alkenes and CH4
d) Cracking or Pyrolysis
When higher alkanes are heated to high temperature 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 :
d) Isomerization
Is the molecular rearrangement of one isomer into a mixture containing
one or more isomers. Alkanes are readily isomerized by strong Lewis acid
catalyst such as AlCl3 or AlBr3 at 25 oC