Physical Properties of

Alkanes
 Boiling Points of Alkanes

governed by strength of intermolecular attractive

forces
alkanes are nonpolar, so dipole-dipole and dipole-
induced dipole forces are absent
 Boiling Point

decrease with chain branching

branched molecules are more compact with
smaller surface area.

Octane: bp 125°C

2-Methylheptane: bp 118°C

2,2,3,3-Tetramethylbutane: bp 107°C
Method of preparation of alkanes
• A. from compounds containing the same number of carbon atoms :
1.reduction of alkyl halides (R-X)
Reduction takes place with (Zn\HCl), (Mg\Hg\EtOH or pd /H2

2.reduction of alcohol
 3.Reduction of ketone or aldehyde
(The reaction involve the conversion of carbonyl group to methylene group)
A. Clemenson reduction (in acid media)

b. Wolff-Kishner reduction (in base media)

4.Catalytic hydrogenation of unsaturated hydrocarbon
 5. Hydrolysis of Grignard reagent (RMgX)

Organic compounds in which a metal atom is directly linked to carbon atom are known
organometallic compounds.
6. Coupling alkyl halides with Grignard reagent
7- Decarboxylation of mono carboxylic acids and its salts
Reactions of Alkanes

1) Combustion or oxidation of alkanes:

Alkanes undergo combustion reaction with oxygen at high
temperatures to produce carbon dioxide and water. This is why alkanes
are good fuels.
 Reactions of Alkanes

1) Free radical chain reactions: : a radical substitution

reaction
Chlorine or bromine reacts with alkanes in the presence of light
(hν) or high temperatures to give alkyl halides. Usually, this method
gives mixtures of halogenated compounds containing mono-, di-, tri-
and tetra-halides.
A free radical chain reaction is also called a radical substitution
reaction, because radicals are involved as intermediates, and the
end result is the substitution of a halogen atom for one of the
hydrogen atoms of alkane.

h CH3Cl + HCl
CH4 + Cl2
Cl2
CH2Cl2 + HCl

Cl2
CHCl3 + HCl
Cl2
CCl4 + HCl
Reactions of Alkanes

2) Free radical chain reactions:

Steps:
I. Initiation:
h 2 Cl
Cl Cl
chlorine chlorine radicals

II. Propagation:

III. Termination:
Selectivity and reactivity of Alkanes
Free radical chain reactions:
Bromination of alkanes follows the same mechanism as
chlorination. The only difference is the reactivity of the radical; i.e., the
chlorine radical is much more reactive than the bromine radical.
Thus, the chlorine radical is much less selective than the bromine
radical, and it is a useful reaction when there is only one kind of
hydrogen in the molecule.
 Relative stabilities of radicals

❖ The more stable a radical, the faster it can be formed. Therefore, a hydrogen
atom, is substituted more selectively in the halogenation reaction.