Reactions of Alkanes IB

Combustion of alkanes
Alkanes are unreactive as a family because of the strong CC and CH bonds as well as them being nonpolar compounds. At room temperature alkanes do not react with acids, bases, or strong oxidizing agents. Alkanes do undergo combustion in air (making them good fuels): 2C2H6(g) + 7O2(g) 4CO2(g) + 6H2O(l) H = 2855 kJ Complete combustion produced carbon dioxide and water while incomplete may produces a combination of carbon monoxide, carbon and water in addition to carbon dioxide. Carbon dioxide contributes to global warming while carbon monoxide is toxic; hemoglobin binds to carbon monoxide in preference to oxygen causing suffocation and even death.

Products of combustion
Complete combustion produces: carbon dioxide water vapour while incomplete may produces a combination of : carbon monoxide carbon water vapour carbon dioxide. Carbon dioxide contributes to global warming. Carbon monoxide is toxic; hemoglobin binds to carbon monoxide in preference to oxygen causing suffocation and even death.

Substitution Reaction
In the presence of light alkanes undergo substitution reaction with halogens. RH + Br2 RBr + HBr In a substitution reaction, one atom of a molecule is removed and replaced or substituted by another atom or group of atoms. Mechanism of subtitution reaction involves free radicals.

Free Radical Substitution reaction

CH3CH 2 CH 2CH 2CH 2CH 3 + Br2 CH 3CH 2CH 2CH 2CH 2CH 2Br + HBr
1-bromohexane
UV

For a reaction between an alkane and bromine to occur, C-H and Br-Br bonds must break. The C-H bond is stronger than Br-Br bond (check bond enthalpy in databooklet). Therefore, the reaction proceeds by first the breakage of Br-Br bond, which is brought about by UV light. Br-Br bond can be broken in one of two ways.

. Br2 2Br g
UV
or

Br2 Br : + Br

UV

Free Radical Substitution reaction

When the bond is broken, either the bond pair can be equally shared between the two atoms producing two bromine atoms (called free radicals), or The bond pair goes with one atom producing a positive and a negatively charged ions of bromine. The first type of bond breakage producing free radicals is referred to as a homolytic fission and the second heterolytic fission. Homolytic fission because the bond pairs are equally distributed, or particles that are the same in every way is produced. homolytic fission of the halogen takes place. In the next step, the free radical removes a hydrogen atom from the alkane forming hydrogen bromine and a free radical of the alkane. CH3CH2CH2CH2CH2CH2-H + Br CH3CH2CH2CH2CH2CH2 + HBr

Free Radical Substitution reaction

The free radical goes on to react with a molecule of chlorine and regenerate another chlorine free radical. CH3CH2CH2CH2CH2CH2 + Br2 CH3CH2CH2CH2CH2CH2Br + Br And so on. Because this reaction, once initiated, can keep itself going is referred to as a chain reaction. The reaction can conducted with any halogen and the mechanism would be the same. Not only that, more than one hydrogen can be substituted.

CH3CH 2CH 2CH 2CH 2CH 3 + 2Br2 CH 3CH 2CH 2CH 2CH 2CHBr2 + 2HBr
1,1 dibromohexane

UV

Mechanism of chlorination of methane

1. Initiation .. : Cl ..
R E P E A T I N G S T E P S

CHAIN REACTION
.. Cl : .. light 2 .. : Cl . .. a free radical

dissociation
2. Chain Propagation (first step) CH3 H + .. : Cl . .. H .. Cl : .. +

. CH3
methyl radical

hydrogen abstraction
3. Chain Propagation (second step) .. : Cl .. .. Cl : .. .. Cl : ..

. CH3

CH3

.. : Cl . ..

feeds back into step two

Mechanism of chlorination of methane

4. Termination Steps
recombinations

.. 2 : Cl . .. CH3. .. : Cl . ..

.. : Cl ..

.. Cl : ..

. CH 3

CH3CH3 .. : Cl CH3 ..
These steps stop the chain reaction

. CH 3