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Alkanes
NYJC 2014
Alkanes
Lecturers: Ms Joanne Low and Mrs Zhuo (Mdm Tan Shuyun)
Contents
Alkanes (exemplified by ethane)
(i) Free-radical reactions
Hydrocarbons as fuels
Learning Outcomes
Candidates should be able to:
(a) Recognise the general unreactivity of alkanes, including towards polar reagents
(b) Describe the chemistry of alkanes as exemplified by the following reactions of ethane:
(i) Combustion
(ii) Substitution by chlorine and by bromine
(c) Describe the mechanism of free-radical substitution at methyl groups with particular
reference to the initiation, propagation and termination reactions
(d) Recognise the environmental consequences of:
(i) Carbon monoxide, oxides of nitrogen and unburnt hydrocarbons arising from the
internal combustion engine and of their catalytic removal
(ii) Gases that contribute to the enhanced greenhouse effect
1. Introduction
1.1 Alkanes
CH3CH2CH2CH2CH3
Pentane C5H12
Cyclobutane C4H8
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Cyclopentane C5H10
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Alkanes
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nclature
1.2 Nomen
No.
N of C
atoms
IUPAC Name/
N
Molecular formula
Conde
ensed
form
mula
Metha
ane
CH4
CH
H4
Displayed
d formula
H
H
Ethane
C2H6
CH3C
CH3
Propa
ane
C3H8
CH3CH
H2CH3
Butane
C4H10
CH3 (CH
H2)2CH3
182
164
183
88
190
42
138
0.5
Boiling
point /oC
H
C
Melting
point /oC
2-methylp
propane
C4H10
CH(C
CH3)3
160
12
2,2-dimethyylpropane
C5H12
C(CH
H3)4
17
10
94
49
81
cyclopen
ntane
C5H10
H2
C
CH2
H2C
H2C
H2
C
cyclohexan
ne C6H12
H
C
CH2
H
C
H
H
H
H
H
H
H2C
CH2
H2C
CH2
C
H2
H
H
H
H
1.3 Alkyl g
groups
formed
d when one of the hy
ydrogen of the alkane
es is remov
ved
named
d by replaccing ane by
b yl
Aliphatic Alkane
A
neral formula: CnH2n+2
Gen
CH3 H
Methane
CH3CH2 H
Ethan
ne
Alkyl grroup
Ge neral formu
ula: CnH2n+1
CH3
Methyl
CH3CH
H2
Ethy
yl
A
Abbreviatio
on
Genneral symbol: R
Me
CH3CH2CH
C 2 H
Propan
ne
CH3CH2CH
C 2
Propyl
Pr
C
CH3CH2CH2CH2 H
ne
Butan
CH3CH2CH
H2CH2
Buty
yl
Bu
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Et
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Alkanes
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2. Bondiing in Alkanes
Bonding a
and molec
cular struc
cture of allkanes
o carbon in alkanes
s
2.1. Hybridization of
W
What is hyb
bridization
n?
Hybridiisation des
scribes the bonding atoms
a
from
m an atomss point of
view. It involves mixing off atomic orbitals to form
f
new hybrid
orbitals.
bridised state):
s
C* (hyb
1s
fo
our sp3 hyb
brid orbitals
s
How?
e electron in
i the 2s orbital first g
gets excite
ed and it is
s promotedd to the 2p orbital.
1. The
2. Durring hybridisation, on
ne 2s and tthree 2p atomic
a
orbittals are hyybridised (m
mixed) to
3
form
m four sp hybrid orrbitals.
3. The
e four sp3 hybrid
h
orbittals form a tetrahedrral arrange
ement. (Boond angle = 109o)
4. Bon
nding will then occur when the sp3 hybrid orbitals ov
verlap withh orbitals of
o other
atom
ms.
groundstate
g
eC
heat
excitedsttateC
heeat
hybrridisedstateC
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Recall: Ov
verlap of orbitals
o
to
o form bon
nds (Chem
mical bond
ding chaptter)
Sigma
a () bonds
s are formed by head
d-on overllap of orbitals
e formed by
y side-on overlap off orbitals.
Pi () bonds are
All single bonds
s are sigm
ma bonds.
s orbitall of H
on
orbital of C
n
ne sp33 orbit
Example: Ethane (C
C2H6)
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3. Physical Properties
3.1 Boiling point and melting point
C5 C17: liquid
*at room
temperature
>C18: solid
The greater the degree of branching (with the same number of C atoms), the
lower the boiling point.
Name
pentane
2-methylbutane
2,2-dimethylpropane
CH3
Structure
CH3CH2CH2CH2CH3
CH3CHCH2CH3
CH3CCH3
CH3
CH3
36
28
10
130
160
17
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.
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Alkanes
NYJC 2014
3.2 Solubility
Alkanes are:
soluble in non-polar (organic) solvents like CCl4, benzene and ether (R-O-R).
- They can form van der Waals interactions with the non-polar solvent.
- The energy released during the formation of van der Waals forces with the nonpolar solvent is enough to overcome the van der Waals forces between the
alkane molecules and the van der Waals forces between the solvent molecules.
alkane layer
water
layer
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Alkanes
NYJC 2014
4. Chemical Properties
Alkanes do, however, react with oxygen and halogens under appropriate conditions,
like in the presence of ultraviolet light or heat.
(i) 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.
Alkanes burn with a non-luminous blue flame with little or no soot if combustion is
complete.
General equation:
y
y
H2O
CxHy + (x + ) O2 x CO2 +
2
4
4CH4 + 5O2
2CO + 4H2O
C
+ 2H2O
(soot)
2CO + 2C + 4H2O
(soot)
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Alkanes
NYJC 2014
(ii) Substitution
Alkanes react with halogen (e.g. Cl2 and Br2) to form halogenoalkanes (alkyl halides)
when irradiated with ultraviolet light or heated.
No reaction takes place in the dark.
The mechanism for the halogenation reactions of alkanes is known as free radical
substitution.
Type of
reaction
Equation
Reagents
Conditions
Product
Observations
Example:
Write a balanced equation for the reaction of propane with bromine. Indicate clearly the
conditions and observations in this reaction.
C3H8 (g) + Br2 (l) C3H9Br (l) + HBr (g)
Conditions: UV light or heat
Observations: Reddish-brown Br2 turns colourless. White fumes of HBr formed.
Note:
Solvent is CCl4 (used when alkane and halogen is present in different phases)
Example: C3H8 (g) + Br2 (l)
Bromination takes place less readily than chlorination
because weaker C-Br and H-Br bonds are formed. (Refer to Group VII)
Fluorination is dangerously exothermic while iodination is slow and reversible.
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5. Reaction mechanism
A cchemical reaction
r
ta
akes place
e when old
d bonds are
a brokenn and new
w ones are
e
crea
ated.
Bon
nd cleavag
ge or bond fission is tthe breakin
ng of chem
mical bondss.
The
ere are two
o types of bond
b
fissio
on required
d for organic chemistrry mechan
nisms:
i)
ii)
Homollytic fissio
on
Hetero
olytic fission
cals are fo
ormed in ho
omolytic fis
ssion.
Free radic
[Recall: A free radica
al is an ato
om or mole
ecule with an
a unpaireed electron. E.g. Cl]
A free radical is extre
emely reacctive becau
use the unpaired elecctron has a strong
tendency to
t pair up with
w anothe
er electron
n from anotther speciees.
Notte: How yo
ou draw your half a
arrows matter!
Arro
ows mustt start from
m the bon
nd and end
d
at tthe atom to
t clearly show thaat a single
elec
ctron is tra
ansferred from bon
nd to atom
m.
5.2 Hetero
olytic fissiion
Heterolyticc fission te
ends to occcur when one of th
he two bonnded atom
ms is much
h
more elec
ctronegative than th e other. (e
e.g. polar bonds)
When the bond brea
aks, the m
more electrronegative atom takees both th
he bonding
g
electrons to
t form an anion. Th
he counterp
part becom
mes a catio
on.
+
Full arrow
w:
Depicts th
he movem
ment
of an elecctron pair..
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H2 Chemistry 9647
Alkanes
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4
D
Description
Initiattion
Cl bond under UV radiation to form
f
free Cl rad
dicals.
Homolyytic fission of Cl
uv
Cl
u.v.
Cl
Cl
Cl
vourable?
Why is this step not fav
CH3CH
H3
CH
H3CH2 + H
C-H bo
onds in alkanes are
a not broken as
a the C-H bond is much stronge
er than the Cl-Cl bond.
-1
-1
Note: B
BE(Cl-Cl) = 242 kJmol , BE(C-H
H) = 435 kJmol
Propa
agation
Cl + CH3CH2H
CH3CH2 + HCl
CH3CH
C 2Cl + Cl
CH3CH2 + ClCl
The e
ethyl radical reacts with a chlorrine molecule to
o produce chloro
oethane and a chlorine
c
radica
al.
The tw
wo steps are re
epeated till all th
he reactants hav
ve been used up or when radic
cals are
destro
oyed i.e. termina
ation step.
Termiination
CH3CH2 +
CH3CH2Cl
Cl
Cl + Cl
CH3CH2 + CH3CH2
ClCl
H3
CH3CH2CH2CH
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NYJC 2014
4
Exam
mple
Exam
mple
The cchlorination of p
propane in the presence of a limited amoun
nt of Cl2 1-cho
olorocyclohexane can be made from cycloh
hexane. Descrribe the
formss 2-chloroprop
pane as a possible pro
oduct. Suggest the reaction mechanism
m of its formatio
on.
mech
hanism of the re
eaction.
Free radical substiitution
Initiation
Cl
Cl
In
nitiation
u.vv.
Cl
Cl
Cl
Cl
u.vv.
Cl
Cl
Prropagation
Cl
HCl
Cl
Cl
Cl2
Te
ermination
Cl
C
Cl
Cl2
Cl
Cl
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NYJC 2014
5.4.1 Multti-substitu
ution
Depen
nding on th
he relative amounts o
of halogen and alkane present and the tim
me allowed
d
for rea
action, a mixture of products wi ll be obtain
ned.
The re
eaction of CH
C 4 and Cl
C 2 is able to
o yield a mixture
m
of CH
C 3Cl, CH2 Cl2, CHCl3 and CCl4:
Examplle
A possible producct for the chlorinatio
c
n of ethan
ne in the presence
p
oof excess chlorine iss
1,1-dich
hloroethan
ne. Sugges
st the mecchanism of the reactio
on.
Mechan
nism: Free Radical Substitutio
S
on
Initiatio
on
uv/ heat
Cl
C
Cl
Propagation
C
Cl + Cl
Termina
ation
(**Write a
at least 3, in
ncluding forrmation of t he halogen, product an
nd one posssible side product)
PPage12of18
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Alkanes
NYJC 2014
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
have the same chemical environment which will lead to the formation of a specific
product. (probability)
Example:
Draw all the possible monosubstituted products when a mixture of 2-methylbutane and
bromine is allowed to react in the presence of sunlight. State the ratio in which they are
formed.
Hd
Hd
Ha
Hb
Hc
Hb
Hc
Hd
Hd
Hc
Hd
Hd
Br
Br
Br
Br
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Alkanes
NYJC 2014
Example:
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
=
=
6
3
Br
:
:
4
2
:
:
Br
2
1
a) Draw the displayed formula of another isomer of C5H12 which reacts with bromine to
form only one monobrominated product.
H
H
H
C
H
Ans:
C
H
C
H
H
C
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Pollutants
Carbon
monoxide
Oxides of
nitrogen
(NO2, NO)
Formation in
car engine
Incomplete
combustion of
fuel
Reaction of N2
with O2 at high
temperatures
Incomplete
Unburnt
hydrocarbon combustion of
fuel
Environmental/
Health Impact
Combines irreversibly
with haemoglobin and
makes it ineffective
as oxygen carrier in
the human body
suffocation or
blood poisoning
Catalyzes formation
of acid rain
Forms smog
Forms smog
Conversion of NO to N2
Pt
2NO(g) N2(g) + O2(g)
2NO(g) + 2CO(g)
N2(g) + 2CO2(g)
Oxidation of unburnt hydrocarbon to
CO2 and H2O
e.g. 2C8H18(l) + 25O2(g)
Pt
16CO2(g) + 18H2O(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.
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Alkanes
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Non-polar
Consisting of molecules held together by weak intermolecular van der Waals forces.
Soluble in non-polar (organic) solvents
Insoluble in polar solvents
Boiling point increases with number of carbons
o Number of electrons in the molecule increases.
o Polarisability increases,
o Strength of intermolecular van der Waals forces increases.
o More energy is required.
Branching decreases the boiling point.
o More spherical in shape
o Smaller surface areas of contact between molecules
o Strength of intermolecular van der Waals forces decreases
o Less energy is required
Alkanes are unreactive because the C-H bond is non polar and relatively strong.
Carbon atoms in alkanes form four sp3 hybrid orbitals from hybridization of one 2s and three 2p
orbitals.
They form 4 sigma bonds () via head-on overlap of orbitals.
Complete combustion of alkanes produces carbon dioxide(CO2) and water(H2O).
Alkanes undergo reactions by a mechanism called free-radical substitution in the presence of
ultraviolet light or heat.
o
Cl
u.v.
(2) Propagation
Equations:1st step - Cl
2nd step - CH3CH2
Cl
2CH3 CHH
2
Cl
(3) Termination
CH 3CH2
Equations:
Cl
CH 3CH2
Cl
CH3CH2
Cl
Cl
Cl
Cl
CH 3CH2
CH 3CH2
Cl
Cl
CH 3CH2
CH2 CH 3
HCl
Cl
Cl
2 Types of
Bond Fission
Occurs between
atoms of _______
electronegativities
(1) Homolytic
fission
Similar
Radicals
Different
Both electrons go to
more EN atom
Cation + Anion
(2) Heterolytic
fission
Page16of18
CH3CH2
Arrows
Products
H2 Chemistry 9647
Alkanes
NYJC 2014
Figure 1. Fractional distillation of crude oil. The fractionating column is cooler at the top than
at the bottom because the fractions at the top have lower boiling points than the fractions at
the bottom.
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H2 Chemistry 9647
Alkanes
NYJC 2014
Length of Carbon
Uses
chain
Refinery
C1-C4
Gasoline
C5-C12
Kerosene
C12-C18
Diesel Oil
C18-C25
gases
heating
Residue
> C25
In a cylinder of a motor car engine, a mixture of petrol vapour (mostly C5 to C10 alkanes)
and the air is ignited by an electric spark, producing an explosive reaction which drives
the piston down.
Petrol rich in straight-chain alkanes (e.g. heptane) ignites very readily and explodes
rapidly, causing knocking of the engine and inefficient combustion.
Combustion of branch-chain alkanes (e.g. 2,2,4-trimethylpentane) is much smoother and
more controlled. It is a more efficient fuel and less likely to cause knocking.
A numerical representation of the antiknock properties of motor fuel, compared with a
standard reference fuel.
Heptane is assigned an octane number of 0.
2,2,4-trimethylpentane (iso-octane) is assigned an octane number of 100.
The octane number of a petrol is found by comparing its performance with a mixture of
heptane and 2,2,4-trimethylpentane.
The octane number of a sample of fuel is determined by burning the gasoline in an
engine under controlled conditions, e.g., of spark timing, compression, engine speed,
and load, until a standard level of knock occurs.
Gasoline that have high octane numbers denotes that they have good anti-knock
properties
Reference texts
1. Understanding Chemistry for Advanced level, Ted Lester, Janet Renshaw,
Chapter 19 [540LIS]
2. Chemistry for Advanced Level. Peter Cann, Peter Hughes, Chapter 23 [540CAN]
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