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Alkanes: H2 Chemistry 9647 Alkanes NYJC 2014
Alkanes: H2 Chemistry 9647 Alkanes NYJC 2014
Alkanes: H2 Chemistry 9647 Alkanes NYJC 2014
Alkanes
NYJC 2014
Alkanes
Lecturers: Ms Joanne Low and Mrs Zhou (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
Cyclobutane C4H8
Page1of17
Cyclopentane C5H10
H2 Chemistrry 9647
A
Alkanes
NYJC 2014
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
Butan
ne
CH3CH2CH
H2CH2
Buty
yl
Bu
Page2of17
Et
H2 Chemistrry 9647
A
Alkanes
NYJC 2014
2. Bondiing in Alkanes
Bonding a
and molec
cular struc
cture of allkanes
2.1. Hybridization of
o carbon in alkanes
s
W
What is hyb
bridization
n?
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 hybrid
disation, on
ne 2s and three 2p atomic orb
bitals are hhybridised (mixed) to
o
form
m four sp3 hybrid orrbitals.
3. The
e four sp3 hybrid
h
orbittals form a tetrahedrral arrange
ement. (Boond angle = 109o)
4. Bon
nding will then
t
occurr when the
e sp3 hybrrid orbitals overlap w
with orbita
als of other
atom
ms.
groundstate
g
eC
heat
excitedsttateC
heeat
hybrridisedstateC
Page3of17
H2 Chemistrry 9647
A
Alkanes
NYJC 2014
Recall: Ov
verlap of orbitals
o
to
o form bon
nds (Chem
mical bond
ding chaptter)
Sigma
a () bonds
s are formed by ____
_________
_ overlap of
o orbitals
e formed by
y _______
______ove
erlap of orb
bitals.
Pi () bonds are
s are ____
_________
_ bonds.
All single bonds
s orbitall of H
on
orbital of C
n
ne sp33 orbit
C2H6)
Example: Ethane (C
Page4of17
H2 Chemistry 9647
Alkanes
NYJC 2014
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 ______ number of C atoms), the
______ the boiling point.
Name
pentane
2-methylbutane
2,2-dimethylpropane
CH3
CH3CH2CH2CH2CH3
Structure
CH3CHCH2CH3
CH3CCH3
CH3
CH3
Melting point / C
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 ____________ 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
Page5of17
H2 Chemistry 9647
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
weak interactions
between alkane
and water molecules
Page6of17
H2 Chemistry 9647
Alkanes
NYJC 2014
4. Chemical Properties
Alkanes do, however, react with oxygen and halogens under appropriate conditions,
like in the ________________________ or ____________.
(i) Combustion
Complete combustion
Alkanes burn in ____________ oxygen to form ____________ 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
CxHy + (x + ) O2 x CO2 +
H2O
2
4
19
O2 (g) 6CO2 (g) + 7H2O (l)
2
Incomplete combustion
In a ____________ supply of oxygen, alkanes burn to form ____________, water
and soot (C).
e.g.
4CH4 + 5O2
2CO + 4H2O
C
+ 2H2O
(soot)
2CO + 2C + 4H2O
(soot)
Page7of17
H2 Chemistry 9647
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
______________________________.
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.
Conditions:
Observations:
Note:
Solvent is CCl4 (used when alkane and halogen is present in different phases)
Example: C3H8 (l) + Br2 (g)
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.
Page8of17
H2 Chemistrry 9647
A
Alkanes
NYJC 2014
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 rad
dical is extremely rea
active because the unpaired
u
eelectron ha
as a strong
g
tendency to
t pair up with
w anothe
er electron
n from anotther speciees.
5.2 Hetero
olytic fissiion
Heterolyticc fission te
ends to occcur when one of th
he two bonnded atom
ms is much
h
_________
_____ electtronegativ
ve than the
e other. (e.g. polar boonds)
When the bond brea
aks, the m
more electro
onegative atom takees _______
______ the
e
bonding electrons to
o form an a
anion. The counterpa
art becomees a cation
n.
+
Full arrow
w:
Depicts th
he movem
ment
of an elecctron pair..
Page9of17
H2 Chemistry 9647
Alkanes
NYJC 2014
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
CH3CH2 + HCl
CH3CH
C 2Cl + Cl
+ 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
Page10of17
H2 Chemistry 9647
Alkanes
NYJC 2014
Example
Example
The chlorination of propane in the presence of a limited amount of Cl2 1-cholorocyclohexane can be made from cyclohexane. Describe the
forms 2-chloropropane as a possible product. Suggest the reaction mechanism of its formation.
mechanism of the reaction.
Page11of17
H2 Chemistrry 9647
Alkanes
NYJC 2014
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)
PPage12of17
H2 Chemistry 9647
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
a) Draw the displayed formula of another isomer of C5H12 which reacts with bromine to
form only one monobrominated product.
Ans:
Page13of17
H2 Chemistry 9647
Alkanes
NYJC 2014
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.
Page14of17
H2 Chemistry 9647
Alkanes
NYJC 2014
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
Page15of17
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.
Page16of17
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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