13.

ALKANES

C H E M I S T RY U N I T SK027

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13.1 ALKANES

OBJECTIVES:
1. State the natural sources of alkanes 2. Describe the combustion of alkanes in -excess oxygen -limited oxygen 3. Explain the unreactivity of alkanes 4. Explain the halogenation reaction of alkanes 5. Explain the free radical subsitution mechanism for methane, ethane and propane. 6. Explain the monosubstitution of alkane containing equivalent type of hydrogen atoms as in neopentane
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Nature sources of Alkanes Natural gas crude oil (petroleum)

Natural gas contains primarily methane (70%) and ethane (10%), with some propane (15%). Crude oil is a mixture of liquid alkanes and other hydrocarbons
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Reaction of alkanes with oxygen

Complete combustion (in excess of oxygen) of alkanes to give carbon dioxide gas, water and heat. CH4 + 2O2 CO2 + 2H2O + heat + 3H2O + heat

C2H6 + 7/2 O2

2CO2

In limited supply of oxygen, combustion of alkanes produces carbon monoxide and water. CH4 + O2 CO + 2H2O + heat 2CO + 3H2O + heat

C2H6 + 5/2O2

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Chemical Properties of Alkanes

Alkanes are nonreactive (inert) towards most reagents such as acids, alkalis, oxidising agents or reducing agents because: are saturated hydrocarbons with no functional group; do not undergo addition reactions. are non-polar, electronegativity values of C & H almost similar. have strong C C and C H covalent bonds have no unpaired electrons. However under right conditions, alkanes may undergo substitution rxn e.g.halogenation.

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13.1 ALKANES

Halogenation of Alkanes
Alkanes react with halogens to produce haloalkanes in the presence of light or when heated. hv

RH + X2

RX + HX

or
Example:

hv

CH4 + Cl2

CH3Cl + HCl

The halogenation is a free-radical substitution reaction. The mechanism involves initiation, propagation and termination steps. In the example; If CH3Cl is allowed to react with more chlorine, further chlorination produces mixture of CH2Cl2,CHCl3 & CCl4.

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Mechanism : Chlorination of methane

The equation of reaction is;

CH4 + Cl2
Mechanism

hv

CH3Cl + HCl

Step 1 : Chain initiation step: In the presence of ultra-violet light / heat, the covalent bond in the chlorine molecule undergoes homolytic fission to produce chlorine free radicals, Cl.

heat
Cl Cl Cl

Cl

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Mechanism : Chlorination of methane

Step 2 : Chain propagation step:
H3C
CH3

+
+
Cl

Cl
Cl

CH3
CH3Cl

+
+

HCl
Cl

These involve reaction between a free radical species (Cl) and a molecule (CH4) to produce a new free radical species (CH3). CH3 propagates a chain reaction when it reacts with another chlorine molecule to form CH3Cl and Cl
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Mechanism : Chlorination of methane

Step 3 : Chain termination step:
Cl

+
+

Cl
Cl

Cl2
CH3Cl

CH3

CH3

+ CH3

CH3CH3

The chain is terminated when two free radicals combine to form molecules.
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CHAPTER 13: HYDROCARBONS

13.1 ALKANES Note: in excess of chlorine, the propagation steps proceed with the reaction between chlorine free radical with chloromethane to produce dichloromethane. The reaction may continue to produce trichloromethane and finally tetrachloromethane. 2nd propagation

CH3Cl + Cl CH2Cl + HCl CH2Cl + Cl2 CH2Cl2 + Cl CH2Cl2 + Cl CHCl2 + HCl

3rd propagation

CHCl2 + Cl2 CHCl3 + Cl CHCl3 + Cl CCl3 + HCl CCl3 + Cl2 CCl4 + Cl

4th

propagation

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Product of monochlorination of alkanes

CH4 + Cl2 hv
methane

CH3Cl + HCl

CH3CH3 + Cl2
ethane

hv

CH3CH2Cl + HCl

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Product of monochlorination of alkanes

CH3CH3CH3 + Cl2 hv
propane

CH3CH2CH2Cl + CH3CHClCH3 + HCl

CH3

CH3 H3C C CH3 CH3

neopentane

+ Cl2

hv

H3C

C CH2Cl CH3

+ HCl

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Bromination of alkanes
Bromine is less reactive toward alkanes than chlorine. Therefore bromine is more selective. The % product yield is based on the stability of the free radical, 3o > 2o > 1o.
CH3 H3C C H CH3

CH3

CH3

+ Br2

h 127oC

H3C C Br

CH3

H3C C H

CH2Br

>99 % (major)
CH3 H3C C H CH3

trace (minor)
CH3

CH3

+ Cl2

h 25oC

H3C C Cl

CH3

H3C C H

CH2Cl

37 %

63 %

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Halogenation of alkanes The difference in selectivity between chlorination and bromination of alkanes need to be kept in mind when one wishes to prepare an alkyl halide from an alkane: 1. Because chlorination of an alkane yields every possible monochloride, it is used only when all the hydrogen in an alkane are equivalent. 2. Bromination is normally used only to prepare tertiary alkyl bromides from alkanes.
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Exercises: When a few drops of liquid bromine are added to neopentane and the mixture is exposed to sunlight, a reaction occurs. a) State two observations that prove that a reaction has indeed occurred. b) Write the chemical equation for the reaction between bromine and neopentane. c) Write the mechanism for the reaction.

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Exercises: Write the equation and mechanism for mono substitution reaction; chlorination of propane to yield 2-chloropropane.

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