Alkanes

1. Introduction
1.1 Alkanes

belongs to a homologous series of hydrocarbons (contain C and H atoms only)
are saturated (C-H and C-C bonds only, hence they contain maximum number of
hydrogens per carbon atoms)
Aliphatic alkanes (open-chained alkanes) Alicyclic alkanes (closed-chained alkanes)


General formula: C
n
H
2n+2
General formula: C
n
H
2n


E.g.


Pentane C
5
H
12






Cyclobutane C
4
H
8
Cyclopentane C
5
H
10































1.2 Alkyl groups
formed when one of the hydrogen of the alkanes is removed
named by replacing ane by yl

Alkane Alkyl group Abbreviation


General formula:
C
n
H
2n+2

General formula:
C
n
H
2n+1

General symbol:
R


CH
3
H CH
3
Me

Methane Methyl


CH
3
CH
2
H CH
3
CH
2
Et

Ethane Ethyl


CH
3
CH
2
CH
2
H CH
3
CH
2
CH
2
Pr

Propane Propyl


CH
3
CH
2
CH
2
CH
2
H CH
3
CH
2
CH
2
CH
2
Bu

Butane Butyl



1.3 Nomenclature




No. of
IUPAC Name/

Condensed
Melting Boiling


C

Displayed
formula

point point


Molecular formula

formula


atoms /
o
C /
o
C

H

1
Methane

CH
4


182 164


H

C

H


CH
4




H
H H

2
Ethane

CH
3
CH
3


183 88


H

C

C

H


C
2
H
6




H H
H H H

3

Propane

CH
3
CH
2
CH
3


190 42


H

C

C

C

H


C
3
H
8




H H H
H H H H

4

Butane

CH
3
(CH
2
)
2
CH
3


138 0.5


H

C

C

C

C

H


C4H10




H H H H

4

2-
methylpropane
CH(CH
3
)
3


160 12


C4H10







5
2,2-dimethylpropane
C(CH
3
)
4


17 10


C5H12






H
2
H H
H



C

H

C


cyclopentane


5

H C CH
2


H
C C
H

94 49



C5H10
2

C C

H
2
C CH
2


H


H



H H

H
2
H H

C H
C
H



6

cyclohexane C
6
H
12

H
2
C

CH
2


H
C

C

H

7 81






H
2
C CH
2


H

C
C

C

H










C

H

H



H
2
H H

2. Bonding in alkanes



Bonding and molecular structure of alkanes
o C has 4 valence electrons and it has electron configuration: 1s
2
2s
2
2p
2
.
o C atoms share electrons by forming 4 covalent bonds to achieve noble gas
electronic configuration.
o Shape of the molecule with respect to carbon: Tetrahedral (4bp, 0lp)




Why does it form a tetrahedral arrangement?


o The concept of hybridisation is useful in explaining the shape of molecular orbitals
for molecules.
o Hybridisation describes the bonding atoms from an atoms point of view. It involves
mixing of atomic orbitals to form new hybrid orbitals.



2.1. Hybridization of Carbon in alkanes

1. The electron in the 2s orbital first gets excited and it is promoted to the 2p orbital.

2. During hybridisation, one 2s and three 2p atomic orbitals are hybridised (mixed)
to form four sp
3
hybrid orbitals.
3. The four sp
3
hybrid orbitals form a tetrahedral arrangement. (Bond angle = 109
o
)
4. Bonding will then occur when the sp
3
hybrid orbitals overlap with orbitals of
other atoms.

1s 2s 2p


C (ground state):









Heat
2s

2p

1s


C* (excited state):












Hybridisation



3



one sp orbital of C




C* (hybridised state):


1s four sp
3
hybrid orbitals


Bonding: Overlap of orbitals to form bonds
Sigma () bonds are formed by head-on overlap of orbitals
Pi () bonds are formed by side-on overlap of orbitals.
All single bonds are sigma bonds.


2.2. Methane (CH
4
)


During hybridisation, one 2s and three 2p atomic orbitals are hybridised (mixed) to form
four sp
3
hybrid orbitals.
Each sp
3
hybrid orbital will overlap head-on with one of the 1s orbitals of four H atoms.
four CH bonds are formed.







one
sp
3
orbital of C




s orbital of H







2.3. Ethane (C
2
H
6
)
The C atom also forms four sp
3
hybrid orbitals.
The tetrahedral carbon atoms form a CC bond by head-on overlapping of one sp
3

orbital from each C atom.
The remaining sp
3
orbitals of carbon form CH bonds by head-on overlapping with a
1s orbital of hydrogen atom.


s orbitals of H
109
o







orbital
s of C


















3. Physical properties



Alkanes:
are non-polar
o C H bond is non-polar as C and H only differ slightly in electronegativity;
o Have a simple molecular structure consisting of alkane molecules held
together by weak van der Waals forces.


3.1 Solubility

Alkanes:
are soluble in non-polar (organic) solvents like CCl
4
and ether.
o Due to similar attractions between molecules (van der Waals forces)
are insoluble in polar solvents like water.
o As it cannot form H-bonds with water.

Please note that alkane layer is on top of water layer as density of alkanes (liquid)
is lower than that of water.

























Alkanes:
are insoluble in polar solvent like water because
o alkane molecules can only interact with water molecules via weak van der
Waals bonds
o which are not strong enough to cause the hydrogen bonds between the
water molecules to break








3.2 Boiling point and melting point

Alkanes have relatively low boiling and melting points.
- Boiling or melting involves overcoming the weak van der Waals forces
between the alkane molecules.



What are the 2 factors affecting strength of van der Waals forces?
[1] The number of electrons within the molecule

[2] Shape/Branching



Boiling point and melting point generally increase with an increasing number of C
atoms:
Alkanes from C1 to C4 are gases, C5 to C17 are liquids while C18 are solids at room
temperature.
- When M
r
increases, number of electrons increases
- Electron cloud becomes more polarisable
- Strength of intermolecular van der Waals forces increases
- More energy is required to overcome the intermolecular forces

Effect of branching on boiling point and melting point for alkanes with the same
number of C atoms
CH
3


CH
3
CH
2
CH
2
CH
2
CH
3

CH
3
CHCH
2
CH
3



CH
3


CCH
3






CH
3


CH
3


Name pentane 2-methylbutane 2,2-dimethylpropane

Boiling point /
o
C 36 28 10
* Melting point /
o
C 130 160 17

Why does a more highly branched alkane have a lower boiling point?

- Highly branched alkanes are more spherical in shape
- Smaller surface area of contact between molecules
- Strength of intermolecular van der Waals forces decreases
- Less energy is required to overcome the intermolecular forces

The greater the degree of branching, the lower the boiling point

Why is the trend for melting point less regular than that of boiling point?

- Branched alkanes can have lower or higher melting points than the straight chain
alkanes depending on the packing of the molecules in the solid
- Highly symmetrical branched alkanes allow the molecules to be packed more
efficiently in the solid and hence have unusually high melting point




4. Chemical properties

Alkanes are saturated and are generally unreactive because:

(i) The C-H bond is non-polar
They have no centres of electrical charge to act as electrophiles or nucleophiles to
attract polar reagents like H
+
, OH
-
or MnO
4
-
.

(ii) The C-C and C-H bonds are relatively strong
C C: 350 kJ mol
-1

C H: 410 kJ mol
-1



Alkanes, however, do react under suitable conditions, like in the presence of
ultraviolet light or heat.


Alkanes undergo two main types of reactions:
(i) Combustion (ii) Substitution.

4.1 Combustion

Complete combustion
Alkanes burn in excess oxygen to form carbon dioxide and water. This reaction is very
exothermic, which accounts for their use as fuels.

General equation:
C
x
H
y
+ (x +
y
) O
2
x CO
2
+
y
H
2
O

4 2



Incomplete combustion
In a limited supply of oxygen, alkanes burn to form carbon monoxide and water.
e.g. 2CH
4
+ 3O
2
2CO + 4H
2
O



Example 1: Write a balance equation for the complete combustion of hexane.
C
6
H
14
(l) +
19
O
2
(g) 6CO
2
(g) + 7H
2
O (l)
2










4.2 Substitution (Halogenation)

Reaction Equation:
C
2
H
6
(g) + Cl
2
(g) C
2
H
5
Cl (g) + HCl (g)

Reagents Cl
2

Conditions Ultra-violet light or sunlight (No halogenation takes
place in the dark.) (OR)

Heat may be supplied to initiate the reaction. Reaction
proceeds very slowly at room temperature.

Product chloroalkanes
Observations Yellowish-green colour of Cl
2
decolourises.
White fumes of HCl produced.


The mechanism for the halogenation reactions of alkanes is known as free radical
substitution.

Example 2: Write a balanced equation for the reaction of pentane with bromine. Indicate
clearly the conditions and observations in this reaction.

C
5
H
12
(l) + Br
2
(l) C
5
H
11
Br (l) + HBr (g)





Conditions: UV light or heat

Observations: Reddish-brown Br
2
gas turns colourless. White fumes of HBr formed.



Note:
- Solvent is CCl
4
(used when alkane and halogen is present in different
phases) Example: C
5
H
12
(l) + Cl
2
(g)
- Further substitutions are also possible: CH
3
CHBr
2
, CH
2
BrCH
2
Br, etc.
- Bromination takes place less readily than chlorination because bromine is
less reactive than chlorine. (Refer to Group VII)
- Fluorination is dangerously exothermic while iodination is slow and reversible.

















5. Reaction mechanisms
5.1 Use of Curly Arrows

Curly arrows are used in mechanisms to represent movement of electrons.
Direction:
Arrow tail is where the electron(s) starts from (bond or lone pair).
Arrowhead is where the electron(s) end up.
Arrow head:
Full arrow shows the movement of an electron pair.
Half arrow shows the movement of a single electron.



5.2 Bond Fission

In organic chemistry mechanisms, bonds can be broken by (1) homolytic fission or
(2) heterolytic fission.


Homolytic Fission

Homolytic fission tends to occur when the two bonded atoms are identical or have
similar electronegativities.
When the bond breaks, each of the bonded atoms takes one of the bonding electrons:




Half arrow:







Free radicals are formed in homolytic fission. [Recall: A free radical is an atom or
molecule with an unpaired electron.]
A free radical is extremely reactive because the unpaired electron has a strong tendency
to pair up with another electron from another species.


Heterolytic fission

Heterolytic fission tends to occur when one of the two bonded atoms is much more
electronegative than the other. (e.g. polar bonds)
When the bond breaks, the more electronegative atom takes both the bonding electrons
to form an anion. The counterpart becomes a cation.


Full arrow:








5.4. Problems with Free-Radical Substitution

In reality, a pure sample of the chloroalkane (or bromoalkane) is seldom obtained because
of the following problems:

(I) Multi-substitution
Depending on the relative amounts of halogen and alkane present and the time allowed
for reaction, a mixture of products will be obtained.
The reaction of CH
4
and Cl
2
is able to yield a mixture of CH
3
Cl, CH
2
Cl
2
, CHCl
3
and CCl
4
:




















CH
3
Cl predominates when there is excess CH
4
; CCl
4
predominates when there
is excess Cl
2
.
To avoid multisubstitution, use an excess of alkane (maximize probability that Cl
attacks CH
4
)

(II) Isomeric Products
In the case of alkanes with 3C, isomeric products are formed depending upon which
H atom is replaced.














Expected Ratio: 10% 90%


A simplified way to obtain the expected ratios is to count the number of hydrogens that
can be substituted that will lead to the formation of the particular product (probability)


Example 3
A possible product for the chlorination of ethane in the presence of excess chlorine is
1,1-dichloroethane. Write equations to show the mechanism of the reaction.

Mechanism: Free Radical Substitution
Step 1: Initiation
uv/ heat
Cl Cl Cl + Cl

Step 2: Propagation












Step 3: Termination
(Write at least 3, including formation of the halogen, product and one possible side
product)








Example 4
a) Draw all the possible monosubstituted products when a mixture of pentane and
bromine is allowed to react in the presence of sunlight. State the ratio in which
they are formed.
Br HHHH HBr HHH HHBr HH



H C C C C C H H C C C C C H H C C C C C H



H H H H H H H H H H H H H H H

6:4:2 = 3:2:1


b) Draw the displayed formula of another isomer of pentane which reacts with bromine to
form only one monobrominated product.
H
H
d
H
a

H
b
H
c


H

C

H
H

C C

C C H
c




H

H
Not the answer:


Another isomer,



H
d


H
b
H
c


H C C

C H




2-methylbutane will









H

H result in 4 different


H
d

C

Hd


monobrominated



H

C

H



products

Ans:

H
d



H



6. Environmental Concern (Refer to Heterogenous catalysis in Kinetics, Page 30)

There are several environmental concerns regarding the use of hydrocarbons as fuels.

(i) Pollutants such as carbon monoxide, oxides of nitrogen and unburnt hydrocarbons
(soot) found in car exhaust can be removed from the car engines using catalytic
converter.




















Pollutants
Formation in car Environmental/ Reaction for removal in


engine Health Impact

catalytic converter




Carbon Incomplete Combines Conversion of CO to CO
2


monoxide combustion of fuel irreversibly with
Pt
2CO(g) + O
2
(g) 2CO
2
(g)

hemoglobin and

makes it ineffective

as oxygen carrier

in the human body


Oxides of Reaction of N
2
with Catalyzes Conversion of NO to N
2


nitrogen O
2
at high formation of acid
Pt
2NO(g) N
2
(g) + O
2
(g)

(NO
2
, NO) temperatures rain 2NO(g) + 2CO(g)


Forms smog
N
2
(g) + 2CO
2
(g)




Unburnt Incomplete Forms smog Oxidation of unburnt hydrocarbon

hydrocarbon combustion of fuel to CO
2
and H
2
O

e.g. 2C
8
H
18
(l) + 25O
2
(g)

Pt
16CO
2
(g) + 18H
2
O(l)



Note:
The catalyst in the converters would be poisoned by the lead present in petrol. Therefore,
cars fitted with catalytic converters must use unleaded petrol.

A honeycomb structure is used to maximise the surface area on which catalysed reactions
can take place.

(ii) Carbon dioxide and methane are greenhouse gases responsible for global warming
and climate changes. One of the major sources of carbon dioxide comes from burning of
fossil fuels for energy production; hence there is a need to find alternative fuels for mankind.