VICTORIA JUNIOR COLLEGE

CHEMISTRY DEPARTMENT
Mr Chang Siang Wen [chang.siangwen@vjc.sg]

H2 ORGANIC CHEMISTRY: ALKANES

Lecture Outline Lecture 1 2
Pages 1–8 8–15
1 Introduction Complete by 18 Aug 23 Aug
2 Cycloalkanes
Tutorial Qns 1–3 4–7
3 Physical Properties
4 Preparation
5 Reactions
5.1 Combustion
5.11 Limited supply of oxygen
5.12 Unlimited supply / excess of oxygen
5.2 Formation of Halogenoalkanes
5.21 Free radical substitution mechanism
5.22 Reactivity of halogens
5.23 Rate of substitution at 1o, 2o and 3o carbon atoms
6 Petroleum and its Environmental Consequences
6.1 Environmental Pollutants
6.2 Use of Catalytic Converter
6.3 Enhanced Greenhouse Effect

Assessment Objectives
Candidates should be able to:

(a) explain 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) free–radical substitution by chlorine and by bromine
(c) describe the mechanism of free–radical substitution 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
(e) recognise that petroleum, a chemical feedstock, is a finite resource and the
importance of recycling

References
1 Chemistry in Action by Michael Freemantle
2 ‘A’ Level Chemistry by E.N. Ramsden
3 Chemistry – Longman ‘A’ Level Guides by J.G.R. Briggs
4 Organic Chemistry by H.L. Heys
5 Organic Chemistry by B.J. Stokes
 Hydrocarbons
(Compounds containing only carbon and hydrogen atoms)

Aromatic hydrocarbon or
Arenes
Aliphatic hydrocarbon Alicyclic hydrocarbon
(Benzene and its alkyl
derivatives)
1. Benzene
1. Cycloalkanes
E.g. cyclohexane

2. Benzene derivatives
E.g. methylbenzene
1. Alkanes 2. Cycloalkenes
2. Alkenes E.g. cyclohexene

3. Naphthalene and others

1 and 2 contain rings of
carbon atoms.

ALKANES

1 Introduction

• Homologous series of saturated aliphatic hydrocarbon of general formula

CnH2n+2.

• Names of alkanes end with ‘ane’.

n molecular formula name structural formula

1 CH4 methane CH4
2 C2H6 ethane CH3CH3
3 C3H8 propane CH3CH2CH3
4 C4H10 butane CH3(CH2)2CH3
5 C5H12 pentane CH3(CH2)3CH3
6 C6H14 hexane CH3(CH2)4CH3

• Constitutional isomerism exists in alkanes containing of more than three

carbon atoms due to branching of chains.

E.g. C4H10 has 2 constitutional isomers.

H
H
H H H H H C H
H
H H
H
H C C C C H
H C
H C C C
C H
C H
H H H H
H
H H H
H H
straight chain branched chain

2
 E.g. C5H12 has 3 constitutional isomers.

H H
H C H H C H
H
H H
H H
H H
H H
H H H H H
H
H C C C C C H H C C C
H C H H C C C H
H H H H H H
H
H H
H H
H H
H H
H C H
straight chain branched chain H

• Nomenclature of branched chain isomer

Prefix – Parent – Suffix

Substituents No. of carbon Functional group

in the longest chain

Step 1: Identify parent chain (longest continuous carbon chain) and name
compound after it.

Step 2: Identify substituent(s) of parent chain which are alkyl group(s)

(general formula: CnH2n+1).

E.g. alkane parent chain substituent(s)

CH 3

CH CH3 butane methyl

CH3 CH22

CH3 CH22 CH22

CH CH CH3 hexane methyl, ethyl

CH3 CH22
CH3

Step 3: Determine position(s) of alkyl group(s) by numbering the carbon

atoms consecutively from one end of parent chain to the other.

(i) Number such that a smaller number is given to the carbon

atom(s) attached to the substituent(s).

E.g. alkane correct name wrong name

CH3
2 4 2–methylbutane 3–methylbutane
1 CH 3 CH3
CH3 CH22

3
E.g. alkane correct name wrong name
6 4 2
CH3 CH22 3 CH22
CH22 CH CH3
5 1
3–ethylhexane 4–ethylhexane

CH22
CH3
8 6
CH3 7 CH2 CH 2 3 CH 3
CH2 CH2 4 CH
5 3–methyloctane 6–methyloctane
2–ethylheptane
CH2
2 CH3
1
(ii) If some alkyl groups occur more than once as substituents, indicate
prefix di–, tri–, tetra–, etc.

E.g. alkane name

CH3
2 4
C 3 CH22 5 2,2–dimethylpentane
1
CH3 CH22 CH3
CH3

CH3 CH3
2,2,4–trimethylpentane
2 4
1 C 3 CH 5 (wrong name: 2,4,4–trimethylpentane)
CH3 CH22 CH3
CH3
(iii) Arrange substituents in alphabetical order, ignoring the prefixes
such as di– or tri–.

E.g.

CH3
CH 3 CH22
4–ethyl–2–methylhexane
4 6 (wrong name: 2–methyl–4–ethylhexane)
2 CH
1 CH CH CH3
CH3 CH22 CH22
3 5
(Wrong name: 3–ethyl–5–methylhexane or 5–methyl–3–ethylhexane. This is
obtained when we numbered from the right. The correct order is the one that gives
the lower number at the first point of substituent.)

4
Self–practice 1 (Check your answers on SLS Alkanes Lesson 1)
Name the following organic compounds using the IUPAC system.

(i) CH3 (ii) CH3 CH3

CH3 CH CH2 CH CH3 CH3 C CH2 C CH2CH2CH3
CH2CH3 CH2CH3 H

2 Cycloalkanes

• Saturated hydrocarbons that contain a ring of carbon atoms are called

cycloalkanes.

• General formula is CnH2n.

E.g.

name structural formula skeletal formula

H22C
H
Cyclopropane CH22
H22C
H

H22C
H CH22
Cyclobutane
H22C
H CH22
H2
C
Cyclopentane
H22C
H C CH2

H22C
H CH2
H2
Methylcyclopentane C H
H
H22C
H C C CH3

H22C
H CH2

CH2 CH2
CH2
Cyclohexane
CH2
CH2 CH2

H2
C H CH3
1,2–dimethylcyclohexane H2C C

H2C CH
C CH3
H2
H
• Chemical behaviour of cycloalkanes is similar to the open–chain alkanes.

5
Making Thinking Visible

Question: Why is it not necessary to name methylcyclopentane as 1–methylcyclopentane?

Answer: Only one substituent on cyclopentane. Hence, position number is not required as
there is no distinction between the carbon atoms.

Question: Why is 1,2–dimethylcyclohexane not named as 3,4–dimethylcyclohexane or

5,6–dimethylcyclohexane?

Answer: The position numbers are chosen to be as low as possible.

You can now attempt Tutorial Questions: Q1 – Q3

3 Physical Properties

I. Solubility, Density and Viscosity

• Alkanes are non–polar. They are insoluble in polar solvents such as water but
soluble in non–polar solvents, such as benzene, ether (e.g. dimethyl ether,
CH3−O−CH3) and CCl4.

Reason: Alkanes do not dissolve in water since the energy released from the
weaker permanent dipole–induced dipole interactions between the polar water
molecules and non–polar alkane molecules is insufficient to overcome the stronger
hydrogen bonding between the water molecules.

• Alkanes float on top of water and thus are less dense than water.

• Viscosity (more viscous, less fluid) of liquid alkanes increases with increasing
molecular mass as long molecules have stronger instantaneous dipole−induced
dipole interactions (due to greater number of electrons).

II. Boiling and Melting Points

(i) Straight chain alkanes

• At room temperature and atmospheric pressure, first four alkanes (C1–C4) are
gases; next thirteen alkanes (C5–C17) are liquids; C18 or more are solids.

Reason: Boiling point increases with number of carbon atoms as more energy
is required to overcome the increasing strength of instantaneous dipole–
induced dipole interactions due to increasing number of electrons.

• Melting point increases in a zig–zag pattern as intermolecular forces in a crystal

depend on the size of the molecules and how well they are packed into the solid
lattice.

(ii) Branched chain isomers

• It has a lower boiling point than the straight chain isomer.

Reason: Branched molecules are more spherical, hence less surface area of
contact between molecules, resulting in a decrease in strength of
instantaneous dipole–induced dipole interactions.

• Effect of branching on packing and on melting point is irregular.

6
4 Preparation

Reduction of Alkenes

Reagent: H2 gas

Condition: Ni catalyst, heat

OR
Pt or Pd catalyst

R' R'' R' R''

+H R'''' C C R'''
2

R'''' R''' H H
alkene alkane

where R’, R’’, R’’’, R’’’’: H or alkyl groups (can be the same or different)
5 Reactions

Candidates should be able to:

(a) explain the general unreactivity of alkanes, including towards polar reagents

• Alkanes form the backbone structure of organic compounds, where other

functional groups are bonded and thereby giving rise to specific reactivity.

E.g.: CH3CH2CH3 propane (alkane)

CH3CH2CH2OH propan–1–ol (alcohol)
CH3CH2CH2Cl 1–chloropropane (halogenoalkane)

• Due to difference in electronegativities between elements, regions of high (δ−)

and low (δ+) electron densities are introduced with addition of functional groups
(e.g. Cδ+–Clδ− and Cδ+=Oδ−).

• However, due to the relatively non–polarity of the C–H bond in alkanes since C
and H have similar electronegativities, electrons in the C–H and C–C bonds
are shared equally by the bonding atoms.

• Hence, none of the atoms in an alkane has any significant charge to attract
charged species like H+, OH− and MnO4−. This renders alkanes to be unreactive
towards polar reagents (e.g. Hδ+Clδ−) and ions.

5.1 Combustion

Candidates should be able to:

(b) describe the chemistry of alkanes as exemplified by the following reactions of
ethane:
(i) combustion

5.11 Limited supply of oxygen

Incomplete combustion produces CO (or C) and H2O.

E.g. CH3CH3 + 5/2 O2 → 2CO + 3H2O

CH3CH3 + 3/2 O2 → 2C + 3H2O

7
 5.12 Unlimited supply / excess of oxygen

Complete combustion produces CO2 and H2O.

E.g. CH3CH3 + 7/2 O2 → 2CO2 + 3H2O

Note:
• Reaction is exothermic. The greater the number of carbon atoms, the
more energy produced but the greater the amount of oxygen needed for
complete combustion.

• Ease of burning accounts for the use of many alkanes as fuels.

• Methane (natural gas or cooking gas) burns with a clean blue flame tinged
with a little yellow. Very little ‘soot’ (carbon) is formed. Burning of higher
alkanes gives rise to sooty flames.

• The complete combustion of hydrocarbons can be expressed with a

general equation:

y y
CxHy + ( x+ ) O2 → xCO2 + ( ) H2O
4 2

Amount of CO2 and H2O produced can be measured and the composition
of hydrocarbon can be calculated.

Making Thinking Visible

Question: Why is it the combustion of alkanes exothermic?

Answer: Stronger bonds in CO2 and H2O are formed and weaker C−H bonds in alkanes
are broken.

Question: Why does the burning of higher alkanes give rise to sooty flames?

Answer: Higher alkanes contain more carbon atoms which need more oxygen to burn.
However, oxygen is limited and incomplete combustion is more likely to take
place leading to formation of soot which is carbon.

5.2 Formation of Halogenoalkanes

Candidates should be able to:

(b) describe the chemistry of alkanes as exemplified by the following reactions of
ethane:
(ii) free–radical substitution by chlorine and by bromine

Alkanes react with halogens (Cl2 or Br2) to produce halogenoalkanes via free–radical
substitution under UV light or under high temperature or heat. One or more of the
hydrogen atoms in the alkane can be substituted by the halogen atoms.

o
UV
300light
C
C H + Cl2 C Cl + HCl
UV light
OR high temp.
alkane OR heat mixture of
halogenoalkanes

8
5.21 Free–radical substitution mechanism

Candidates should be able to:

(c) describe the mechanism of free–radical substitution with particular
reference to the initiation, propagation and termination reactions

• Chain reaction involving three basic steps:

1. Initiation
2. Propagation
3. Termination

E.g. Chlorination of ethane via free–radical substitution mechanism.

CH3CH3 + Cl2 → CH3CH2Cl + HCl

1. Initiation: UV light, high temperature or heat provides energy for

homolytic cleavage of Cl–Cl bond to generate free
radicals, Cl•.

UV light
Cl Cl → 2Cl• radicals created

: The half arrow shows the movement of a single electron.

Cl• radical is very reactive as it has an unpaired electron and seeks to
complete its octet of electrons by pairing up the unpaired electron.

2. Propagation: A Cl• radical is consumed in one step and another Cl•

radical is generated in another step to keep the chain
reaction going.
•
(a) CH3CH3 + Cl• → CH3CH2 + HCl radicals used and
• then regenerated
(b) Cl2 + CH3CH2 → CH3CH2Cl + Cl•

Together, these two propagation steps consume one CH3CH3 and one Cl2, and
produce one HCl and one CH3CH2Cl, giving the following net reaction:
CH3CH3 + Cl2 → CH3CH2Cl + HCl
When one more H atom in CH3CH3 is substituted by Cl, step (a) is repeated
again and then step (b) and so forth. With each repetition of step (b), a
chlorine−substituted molecule is formed.

3. Termination: Free radicals are consumed but not generated.

Possible chain–terminating steps are:

Cl• + Cl• → Cl2

• • radicals removed
CH3CH2 + CH3CH2 → CH3CH2CH2CH3
•
CH3CH2 + Cl• → CH3CH2Cl

Overall:
UV light
CH3CH3 + Cl2 → CH3CH2Cl + HCl

9
 Note:
(i) A single free radical (once formed) can produce a large number of
product molecules by chain reaction sequence.
(ii) Reaction does not stop at monosubstitution. More than one hydrogen
atom in an alkane can be replaced by chlorine with the formation of HCl.

E.g. Chlorination of CH4 via free–radical substitution mechanism.

CH4 + Cl2 → CH3Cl + HCl (monosubstitution)

CH3Cl + Cl2 → CH2Cl2 + HCl (disubstitution)
CH2Cl2 + Cl2 → CHCl3 + HCl (trisubstitution)
CHCl3 + Cl2 → CCl4 + HCl (tetrasubstitution)

Hence, the reaction is not ‘clean’, meaning it does not give a single
organic product but a mixture of products.

(iii) Ethane and higher alkanes give rise to isomeric halogen derivatives
when more than one hydrogen atom is substituted.

E.g. There are two dichloroethanes, CH2ClCH2Cl and CH3CHCl2,

formed from the substitution of ethane with Cl2. This is typical of
reactions of alkanes as there is little difference between the
strengths of the differently situated C–H bonds.

Making Thinking Visible

Question: Why does monosubstituted ethane, CH3CH2Cl, predominate if excess of

ethane is used?

Answer: In the propagation step, there is a higher probability for the Cl• radical to collide
with a CH3CH3 molecule rather than with a CH3CH2Cl molecule. Thus,
considerable amount of CH3CH2Cl will be formed first.
CH3CH3 + Cl2 → CH3CH2Cl + HCl

Question: Why does more highly substituted ethane, such as CCl3CCl3, predominate if
excess of Cl2 is used?

Answer: All the hydrogen atoms in ethane can be substituted by chlorine atoms when
excess Cl2 is used.
CH3CH3 + 6Cl2 → CCl3CCl3 + 6HCl

10
Self–practice 2 (Check your answers on SLS Alkanes Lesson 2)

Write equations to show the mechanism of

CH3CH2CH3 + 2Br2 → CH3CHBrCH2Br + 2HBr

Mechanism:

Initiation:

Propagation:

Termination:

5.22 Reactivity of halogens

Reactivity of halogens with alkanes to form halogenoalkanes (RX) decreases

down Group 17: F2 > Cl2 > Br2 > I2

F2: Reaction proceeds with explosive violence, hence cannot be

used in laboratory.
Cl2 and Br2: Reaction occurs under UV light, high temperature or heat
I2: Least reactive as iodine does not react with alkanes to any
extent.

E.g 1: For CH4 + Cl2 → CH3Cl + HCl ∆Hrxn 1

•
1 propagation step: CH4 + Cl• → CH3 + HCl
st
∆H1(1st)
∆H1(1st) = BE(C–H) – BE(H–Cl)]
= 410 – 431
= –21 kJ mol–1
•
2nd propagation step: CH3 + Cl2 → CH3Cl + Cl• ∆H1(2nd)
∆H1(2nd)= BE(Cl–Cl)] – [BE(C–Cl)
= 244 – 340
= –96 kJ mol–1
∆Hrxn 1 = ∆H1(1st) + ∆H1(2nd)
= –21 – 96
= –117 kJ mol–1

E.g 2: For CH4 + Br2 → CH3Br + HBr ∆Hrxn 2

•
1 propagation step: CH4 + Br• → CH3 + HBr
st
∆H2(1st)
∆H2(1st) = BE(C–H) – BE(H–Br)]
= 410 – 366
= +44 kJ mol–1

11
 •
2nd propagation step: CH3 + Br2 → CH3Br + Br• ∆H2(2nd)
∆H2(2nd) = BE(Br–Br)] – [BE(C–Br)
= 193 – 280
= –87 kJ mol–1
∆Hrxn 2 = ∆H2(1st) + ∆H2(2nd)
= 44 – 87
= –43 kJ mol–1

Reasons:
As shown by the above examples, as the atomic radius of halogen X
increases down the group, the energy released in the formation of H–X bond
in the first propagation step is less than the energy needed to break C–H
bond. Hence, the first propagation step is increasingly endothermic and
there is decreasing ease of substitution since ∆Hrxn becomes less
exothermic down the group.

You can now attempt Tutorial Questions: Q4 – Q5

5.23 Rate of substitution at 1o, 2o and 3o carbon atoms

In higher alkanes, the substitution of hydrogen atoms at different carbon atoms leads
to different products.

E.g. When butane undergoes monochlorination, there are two possibilities for the
substitution to take place as shown below.

H H H H Cl2 H H H H
Cl2
Cl• H C C C C H C C C C Cl Cl•
Cl
Cl
H H H H H H H H
H H H H 1o alkyl radical 1–chlorobutane
H C C C C H expected = 60%
yield = 30%
H H H H
H H H Cl2 H H Cl H
Cl Cl2 H C C C C H Cl•
Cl• H C C C C H Cl
H H H H H H H H
2–chlorobutane
2o alkyl radical
expected = 40%
yield = 70%
Note: Classification of carbon atoms

Carbon atoms are classified as being 1o, 2o or 3o carbon, by the number of carbon
atoms directly bonded to it.

1o carbon 2o carbon 3o carbon 4o carbon

C C
C C C C C C C C C C C
C
Bonded to Bonded to Bonded to Bonded to
one other two other three other four other
C atom C atoms C atoms C atoms

12
Making Thinking Visible
Question: How is the expected yield of 1–chlorobutane and 2–chlorobutane in the
monochlorination of butane obtained?
Answer: Butane has 10 hydrogen atoms. Based on probability factor, hydrogen atoms at
any 6 positions around primary (1o) carbon atoms and any 4 positions
around secondary (2o) carbon atoms can be substituted by halogen atoms.
The expected ratio of 1–chlorobutane to 2–chlorobutane formed is
60% : 40%.

6/10 x 100% = 60%

4/10 x 100% = 40%

Question: Why is there is a discrepancy between the expected ratio and the ratio of the
monochlorinated products obtained experimentally?

Answer: The 2o alkyl radical, which is more stable than the 1o alkyl radical, is formed
preferentially. Hence, the rate of substitution of hydrogen atom at 2o carbon
atom is higher than that at 1o carbon atom. With larger amount of 2o radicals
formed, they will react with Cl2 to form 2–chlorobutane (CH3CH2CHClCH3) as
the major product.

Note: Relative stability of radicals

R R R

H C < R C < R C

H H R

Primary Secondary Tertiary

(1o) radical (2o) radical (3o) radical
Least stable → Most stable

Alkyl groups, R, exert electron donating inductive effect and they can
stabilise a carbon radical by increasing the electron density on the
electron deficient carbon atom carrying the odd electron. The more alkyl
groups bonded to this carbon, the less reactive and more stable the
radical. This explains why the tertiary radical is more stable than the secondary
or primary radical that has fewer alkyl groups.

You can now attempt Tutorial Questions: Q6 – Q7

13
6 Petroleum and its Environmental Consequences

Candidates should be able to:

(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
(e) recognise that petroleum, a chemical feedstock, is a finite resource and the
importance of recycling

Petroleum is a finite resource. At some point in the future the supply of oil in the
Earth’s crust will be exhausted. In addition to being essential for current transportation
technologies, most products manufactured today, from clothing to automobiles to
medical supplies, are derived from petroleum–based products. Hence, it is important to
recycle as much as we can.

6.1 Environmental Pollutants

To achieve maximum power, the internal combustion engine is normally run on an air–
fuel mixture which is 10–20% richer in fuel than the stoichiometric mixture. Hence, car
exhausts emissions contain the following pollutants.

• Carbon monoxide due to incomplete combustion of fuel. CO combines with

haemoglobin in blood and reduces the oxygen–carrying ability of the haemoglobin.
This can lead to oxygen starvation and eventual death.
• Oxides of nitrogen, NO and NO2, formed from the reaction of nitrogen and oxygen
in the car’s engine. These oxides cause smog and acid rain. High levels of NO and
NO2 damage plant life. NO2 also contributes to the formation of acid rain which
damages vegetation, buildings and water bodies.

• Unburnt hydrocarbons due to incomplete combustion of fuel. In strong sunlight it

becomes smog and can cause lung damage.

6.2 Use of Catalytic Converter

In many countries, pollution from motor cars is being reduced by fitting a platinum
catalyst converter onto the motor car exhausts. It catalyses the oxidation of CO and
unburnt hydrocarbons to CO2 and H2O by oxides of nitrogen, NO and NO2 which are
reduced to harmless N2 and O2. The catalytic converter can be ‘poisoned’ by lead
deposits on the catalyst’s surface which block the sites for reactions to take place.
Thus, lead–free petrol should be used.

E.g. hydrocarbons + oxides of nitrogen → carbon dioxide + water + nitrogen

2CO + 2NO → 2CO2 + N2

6.3 Enhanced Greenhouse Effect

The enhanced greenhouse effect is the direct result of human activities. Processes
such as the burning of fossil fuels, industrial operations and forest clearing increase
the amount of carbon dioxide, methane and oxides of nitrogen in the atmosphere.
Chlorofluorocarbons, or CFCs, are also potent greenhouse gases, and as an added
danger, they also destroy the ozone layer. In the upper atmosphere, CFCs produce Cl•
where it catalyses the conversion of ozone into O2. Ozone absorbs uv radiation better
than does O2, so its depletion allows more of this high energy radiation to reach the
Earth's surface.

14
Ultimately, more greenhouse gases means more infrared radiation trapped and held,
which gradually increases the temperature of the Earth’s surface and the air in the
lower atmosphere. The atmosphere is now trapping more heat that would otherwise
have escaped to space. This enhancement of the greenhouse effect is causing global
warming. Of all the greenhouse gases released by man–made processes, carbon
dioxide is the largest individual contributor to the enhanced greenhouse effect,
accounting for about 60% of the increase in heat trapping.

15