H2 Chemistry 9647

Alkanes

Name:
_________________________________
_____________

NYJC 2014

CT: ____________

Date:

Alkanes Tutorial
Section A: Review Questions
1. N2013/1/21
A hydrocarbon on complete combustion produces equal volumes of carbon dioxide and
water vapour. What is the empirical formula of the hydrocarbon?
A
B
C
D

CH
CH2
C2H2
C2H4

Ans: B

y
y
Complete combustion of hydrocarbons:
CxHy + (x + 4 ) O2 x CO2 + 2 H2O
Since all reactants and products are in gaseous state, the volume of gaseous products
are directly proportional to the stoichiometric amounts.
y
Equal volumes of carbon dioxide and water vapour would mean x = 2 . Hence only
options B and D fulfil this equality. Option D is not an empirical formula, therefore option
B is correct.
2. Which of the following statements is correct?
A The boiling points of alkanes increase due to increasing hydrogen bonding as the
size of the molecule increase.
B The boiling points of alkanes increase due to increasing van der Waals forces as the
size of the molecule increase.
C Alkanes with the same molecular formula but with branched chains have higher
boiling points than the corresponding unbranched chain isomers
D All alkanes have the same boiling point as they have the same general formula.
Ans: B
3. N2005/I/22
Why does the reaction between propane and chlorine not give a high yield of
2-chloropropane?
A
B
C
D

A mixture of chlorine and propane cannot be prevented from exploding.

Disubstitution by chorine takes place preferentially to monosubstitution.
The central carbon atom of propane is too weakly nucleophilic.
The chlorine replaces any of the hydrogen atoms in propane.

Ans: D
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NYJC 2014

4. How many different substitution products are, in principle, possible when a mixture of
bromine and ethane is allowed to react in the presence of sunlight?
A
B
C
D

3
5
6
9

Ans: D
Mono-substituted (1-bromoethane)
Di-substituted (1,2-dibromoethane and 1,1-dibromoethane)
Tri-substituted (1,1,1-tribromoethane and 1,1,2-tribromoethane)
Tetra-substituted (1,1,1,2-tetrabromoethane and 1,1,2,2-tetrabromoethane)
Further substitution (1,1,1,2,2-pentabromoethane and 1,1,1,2,2,2-hexabromoethane)
5. N2012/1/20
When heated with chlorine, the hydrocarbon 2,2-dimethylbutane undergoes free radical
substitution. In a propagation step, the free radical X is formed by the loss of one
hydrogen atom.
Hc

Ha

Hc
Hb

Ha
C

Ha

Hb
Hc

Hc
Hc
C

Hc

Hc
C

CH3

CH3CH2

Hc

CH3

Cl

HCl

CH3

Hc

How many different forms of Xare theoretically possible?

A
B
C
D

1
2
3
4

Ans : C
In the 2,2-dimethylbutane molecule, there are 3 different chemical environments of
hydrogen atoms (Ha, Hb,Hc). The radical Xis formed in the propagation step where a
C-H bond undergoes homolytic fission to form in the approximate ratio of :
CH3
CH3

CH2

C
CH3

CH3
CH2CH3

CH

CH3
CH3CH2

CH2

CH3

C
CH3

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CH3

H2 Chemistry 9647

Alkanes

NYJC 2014

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H2 Chemistry 9647

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NYJC 2014

6. Which of the following pollutants is not a product of the combustion of petroleum?

A
B
C
D

Nitrogen dioxide
Carbon dioxide
Carbon monoxide
Hydrogen chloride

Ans : D
7. Which of the following molecules would be present during the free radical chlorination of
methane?
1 hydrogen
2 hydrogen chloride
3 dichloromethane
Ans: C (Options 2 and 3)
In free radical substitution reactions, hydrogen is never obtained as the CH bond
energy is too high.
8. N2013/1/32
The substitution reaction between CH 4(g) and Br2(g) in the presence of ultraviolet light
involves the following steps.
Br2

2Br

CH4

Br

CH2

CH2

Br2

CH3Br

HBr
Br

Why is this called homogeneous catalysis?

1 Bromine radicals are in the same physical state as bromine and methane.
2 Bromine and methane are in the same physical state.
3 The bromine molecule splits into two bromine radicals.
Ans: D (Option 1 only)
Homogeneous catalysis is a sequence of reactions that involve a catalyst in the same
phase as the reactants. The catalyst here is the bromine radical.

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H2 Chemistry 9647

Alkanes

NYJC 2014

9. N2013/1/38
Which of the following hydrocarbons undergo substitution reactions to form only one
monochloro-derivative?
1 cyclobutane
2 2,2-dimethylpropane
3 2-methylpropane
Ans: B (Options 1 and 2)
When cyclobutane and 2,2-dimethylpropane undergo free radical substitution with
chlorine, only one possible product can be formed as all the hydrogen atoms in each
molecule are in the same chemical environment.
H
H

H
H

Ha

Ha

H
H

Hb

Ha
C
H

H
H

Ha

Ha

Ha

Ha

Ha

Ha

When 2-methylpropane undergo free radical substitution with chlorine, two possible
products can be formed as the hydrogen atoms are in two different chemical
environments (Ha, Hb). (Refer to Q7)

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H2 Chemistry 9647

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NYJC 2014

10. Arrange the following hydrocarbons in order of increasing boiling point, giving your
reasons:
(a)octane
(b)2-methylheptane
(c)2,2,3-trimethylpentane
(d)2,2,3,3-tetramethylbutane
(e)3-methyloctane
Order of increasing boiling points: d<c<b<a<e
All the five hydrocarbons have simple molecular structures. Boiling involves overcoming
the weak van de Waals forces between alkane molecules.
3-methyloctane has highest boiling point since it has 9 carbon atoms, compared to the
rest which has 8Cs. Hence, it has the largest number of electron with the most
polarisable electron cloud, giving rise to the strongest van de Waals forces.
For the remaining alkanes, they have the same no. of carbon atoms, hence same no.
of electrons. Hence, the strength of van de Waals depends on the surface area of
contact between molecules.
The more highly branched the alkane, the lower smaller surface areas of contact,
the weaker the strength of the van de Waals forces.
Degree of branching:
octane < 2-methylheptane < 2,2,3-trimethylpentane < 2,2,3,3-tetramethylbutane

<
<
<
Boiling point:
octane > 2-methylheptane > 2,2,3-trimethylpentane > 2,2,3,3-tetramethylbutane

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H2 Chemistry 9647

Alkanes

NYJC 2014

11. Free radical substitution of alkanes to produce haloalkanes (2-chloro-2-methylpropane

and 1-chloro-2-methylpropane) is not synthetically useful since a mixture of products is
normally obtained. Show the mechanism for the formation of both isomeric products.
Suggest, with a reason, the approximate ratio in which they are formed.

(a) Show the mechanism for the formation of 2-chloro-2-methylpropane.

Initiation
uv/ heat
Cl + Cl
Cl
Cl
Propagation
CH3CHCH3 + Cl

CH3CCH3

CH3

CH3CCH3

+ HCl

CH3
Cl

+ Cl2

CH3CCH3 + Cl

CH3

CH3

Termination
Cl + Cl

CH3CCH3

Cl2

Cl

+ Cl

CH3CCH3

CH3
CH3CCH3
CH3

CH3
+ CH3CCH3
CH3

CH3 CH3
CH3C

CCH3

CH3 CH3

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H2 Chemistry 9647

Alkanes

NYJC 2014

(b) Show the mechanism for the formation of 1-chloro-2-methylpropane.

Initiation
uv/ heat
Cl + Cl
Cl
Cl
Propagation

CH3CHCH3 + Cl

CH3CHCH2

CH3
CH3CHCH2 + Cl2

+ HCl

CH3
CH3CHCH2Cl + Cl

CH3

CH3

Termination
Cl + Cl

Cl2

CH3CHCH2 + Cl

CH3CHCH2Cl

CH3

CH3

CH3CHCH2 + CH3CHCH2
CH3

CH3

CH3
CH3CHCH2 CH2CHCH3
CH3

(c) Suggest, with a reason, the approximate ratio in which they are formed.
H

Equation:

Hb
Hb C Hb
Hb
Hb
C
Hb C
C Hb
Hb
Hb
Ha

H
Cl C
+ Cl2

H
C H
H

H
H

H
C

u.v.

H
C

H
C
C
Cl

H
H
C H
H

There is 1 possible H (H a) can be substituted to form 2-chloro-2-methylpropane

while there are 9 possible H (H b) can be substituted to form 1-chloro-2methylpropane.
Hence, ratio of 2-chloro-2-methylpropane : 1-chloro-2-methylpropane = 1:9
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H2 Chemistry 9647

Alkanes

NYJC 2014

12. When 10 cm3 of a gaseous hydrocarbon X were burned in 85 cm3 of oxygen, the final
gaseous mixture contained 40 cm3 of carbon dioxide and 20 cm3 of unreacted oxygen.
[All gaseous volumes measured under identical conditions.]
(a) Determine the formula of hydrocarbon X.
CxHy (g)

+ (x + y/4) O2 (g)

[2]
x CO2 (g)

+ (y/2) H2O (l)

Volume of reacted O2
= 85 20 = 65 cm3
Volume of CO2 produced = 40 cm3
By comparing the mole ratios:
For CxHy (g) and CO2 (g):

1 / x = 10 / 40

=> x = 4

[1]

For CxHy (g) and O2 (g):

1 / (x + y/4) = 10 / 65

=> y = 10

[1]

Hence, the molecular formula of the hydrocarbon, W, is C 4H10.

*W can be butane or 2-methylpropane.
(b) When an excess of X is treated with a small quantity of bromine in the presence of
ultraviolet light, two mono-substituted products are formed.
(i) Identify the two products formed.

[1]

1-bromobutane and 2-bromobutane

[1]

*Alternatively 2-chloro-2-methylpropane and 1-chloro-2-methylpropane

(ii) Suggest, with a reason, the approximate ratio in which they are formed.
[2]
Whe butane is treated with a small quantity of bromine in the presence of ultraviolet light,

Ha

both 1

Ha

Hb

Hb

Ha

Ha

Hb

Hb

Ha

Ha

Br2

uv

Br

Br

HBr
2Total of 6 possible H (Ha) can be substituted to form 1-bromobutane while only
4 possible H (Hb) can be substituted to form 2-bromobutane.
[1]

Hence, ratio of 1-bromobutane:2-bromobutane = 6:4 = 3:2

*Alternatively 2-chloro-2-methylpropane : 1-chloro-2-methylpropane = 1:9
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H2 Chemistry 9647

Alkanes

NYJC 2014

Section B: Discussion Questions

1. N2008/I/21
Use of the Data Booklet is relevant to this question.
On the basis of bond energies, what could be the products of the following reaction?
CH3 + CH3CH2Cl
A
B
C
D

CH4 + CH3CHCl
CH3CH2CH2 + HCl
CH3CH2CH3 + Cl
CH3CH2CH2Cl+ H

A
B

CH4 + CH3CHCl
CH3CH2CH2 + HCl

C
D

CH3CH2CH3 + Cl
CH3CH2CH2Cl+ H

Bonds broken
C-H (+410)
C-Cl (+340)
C-H (+410)
Total = +750
C-Cl (+340)
C-H (+410)

Bonds formed
C-H (-410)
C-C (-350)
H-Cl (-431)

Overall H
0
-31

C-C (-350)
C-C (-350)

-10
+60

To decide which is the most likely step, the first factor is the amount of energy
needed to break the bonds as this is an endothermic process and would pose as
the energy barrier to be overcome before the reaction can occur.
Option C requires the least energy (+340KJmol -1), hence will be the most likely step
that occurs (although it may not be the most exothermic reaction overall).
Option C has the lowest activation barrier.
Note: Should 2 options require the same energy in breaking bonds, the next factor to
consider will be energy released in forming bonds. More energy released in forming
bonds will result in a more exothermic reaction, thus will be more favourable.
2. N2001/I/22
An energy level diagram for a single reaction step is shown below:

To which of the following steps in the reaction of methane with chlorine in the presence
of light does this diagram apply?
A
B
C
D

CH3
CH3
CH3
Cl2

+ CH3
C2H6
+ Cl2

CH3Cl + Cl
+ Cl

CH3Cl

Cl + Cl
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H2 Chemistry 9647

Alkanes

NYJC 2014

Energy of reactants increases when only bond breaking occurs in the reaction.
A and C are bond forming processes and energy should decrease.
B consists of a bond breaking (Cl-Cl) followed by bond forming (H-Cl) and energy should
increase then decrease.
D is the only reaction that depicts a bond breaking process only.
3. N2008/I/24
Non-ionic detergents can be made by reaction of epoxyethane, in an excess, with a
C11 alcohol.
A possible mechanism involves homolytic fission of a C-O bond in epoxyethane giving
rise to a double-ended free radical that initiates a chain reaction. The first propagation
step is as follows:
O
CH2CH2O + H2C CH2 CH2CH2OCH2CH2O
epoxyethane
After termination of the reaction with an alcohol, what is a possible formula of such a
non-ionic detergent?
A
B
C
D

(CH3(CH2)10O)10CH2CH2OH
CH3CH2CH2 + HCl
CH3(CH2)10O(OCH2CH2)10OH
CH3(CH2)10O(CH2CH2O)10H

In each propagation step, the carbon chain in the product extends by -(CH 2CH2O)- i.e. a
double-ended radical (CH2CH2O)n is formed.
Upon termination with a C11 alcohol, the product formed should consist of (CH2CH2O)n and
remaining parts should add up to form a C11 alcohol.
Only option D fulfils the above criteria.

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H2 Chemistry 9647

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NYJC 2014

4. N2006/III/6
(a) State the conditions used for the reaction between ethane and bromine.
C2H6 + Br2 C2H5Br + HBr
Ultra-violet light/heat
(b)

Why is this described as a free-radical substitution reaction?

In the initiation step, a bromine molecule undergoes homolytic fission to produce
two bromine radicals containing an unpaired electron.
The bromine radicals then goes on to replace a hydrogen atom on ethane to form
bromoethane in the propagation steps.

(c)

Explain why this reaction is an example of homogeneous catalysis.

Bromine radicals formed in the initiation stage catalyzes the reaction. The
reactive bromine radicals are subsequently reacted and re-generated in the
propagation steps.
The reaction is a type of homogeneous catalysis as the reactants, products and
catalyst are all in the same phase i.e. liquid phase.

5. N2007/II/1(a),(b),(c)
When an examination paper is given in it will go by air to England. Intercontinental jet
airliners use kerosene as fuel. The formula of kerosene may be taken as C 14H30.
(a) To which homologous series does kerosene belong?
Alkanes.
(The formula agrees with the general formula of alkanes C nH2n+2 with n=14)
(b) When kerosene burns in an excess of air, carbon dioxide and water form. Balance
the following equation for the complete combustion of kerosene.
2 C14H30 + 43 O2 28 CO2 + 30 H2O
(c) The flight path from Singapore to London is approximately 10 700 km. A typical
intercontinental jet airliner burns 10.8 kg of kerosene for each kilometer covered.
(i) Calculate the mass, in tones, of C 14H30 burnt on a flight from Singapore to
London. [1 tonne = 1000 kg] [116 ton]
mC14H30 burnt = 10.8 x 10 700 = 115560 kg
= 116 ton (3sf)

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(ii)

Alkanes

NYJC 2014

Use your equation in (b) to calculate the mass of CO 2 produced during this
flight. [360 ton]

115560 103
14(12.0) 30(1.0)

nC14H30 burnt
nCO2 formed

5.836 105 mol

= 14 nC10 H 40burnt
8.171106 mol

6
mCO2 formed 8.171 10 44.0
3.60 108 g

3.60 105 kg
3.60 102 ton

6. N2007/II/4(g)
Granular urea CO(NH2)2 can be used to remove NO 2 from the flue gases of power
stations where hydrocarbon fuels are burned in air. Carbon dioxide, water and nitrogen
are formed.
(a)Write a balanced equation for this reaction.
4CO(NH2)2

6NO2

4CO2

8H2O

7N2

(b) Why is it important to remove NO2 from the flue gases?

NO2 catalyzes the oxidation of SO2 to SO3. When formed, SO3 can dissolve in water
to form acid rain.
Comments: There were also many students who, wrongly thought NO 2 is
responsible for global warming. Examiners expected answers to be specific, e.g.
NO2 is highly toxic. Answers such as it is a pollutant were considered to be too
vague and not worthy of credit.

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H2 Chemistry 9647

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NYJC 2014

9. Petrol engines in cars produce a number of pollutants which can be removed by

catalytic converters.
Discuss this statement, indicating what the pollutants are, how they arise and how they
are removed as efficiently as possible in a catalytic converter. Write equations for any
reactions you discuss.
Pollutants:
CO from incomplete combustion of fuel
Oxides of nitrogen (NO2, NO) from reaction of N2 with O2 at high temperatures)
Unburnt hydrocarbon Incomplete combustion of fuel
Removal: Catalytic converters contain either a Pt, Rh or Pd catalyst. The pollutants
undergo reactions to form harmless products such as H2O, CO2, N2.
Conversion of CO to CO2: 2CO(g) + O2(g) 2CO2(g)
Conversion of NO to N2:

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) 16CO2(g) + 18H2O(l)

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