Alkanes

Self-Attempt Questions

1* Dichloroethane can be made by the free-radical chlorination of ethane.

(i) Describe the reaction mechanism of its formation, labeling each step in the mechanism
appropriately.

(ii) Suggest one possible by-product of this reaction and how in industry, it may be separated
from dichloroethane.
J98/I/6(c)

2 When 2-methylbutane reacts with chlorine, four different monochlorinated products are produced.

(a) State the type of isomerism shown by the four products

(b) Draw the structural formula of each of the products, and suggest with a reason (probability
factor), in what ratio they might be formed.

(c) For 2-methylbutane, the order of reactivity of tertiary, secondary and primary hydrogen
atoms follows a 5:4:1 ratio. Predict the ratio in which the above monochlorinated products
are formed taking into account the reactivity of the different types of hydrogen.

3* (a) Crude oil is the principal source of hydrocarbons. Thermal cracking of crude oil is carried out
to give smaller chain hydrocarbons which are more useful.

Three possible hydrocarbons that can be derived from crude oil are shown below.

but-1-ene hexane 2,2-dimethylbutane

Mr = 56.0 Mr = 86.0 Mr = 86.0
(i) Arrange these three compounds in order of increasing boiling points and explain your
answer.

(ii) Predict, with reasons, whether pentan-3-one (Mr = 86.0) will have a higher boiling
point compared to hexane.

pentan-3-one
[5]

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 (b) Hexane undergo reactions with bromine under controlled conditions to form the
monobrominated product.

Briefly state the reaction of bromine with hexane.

Your answer should
 name the types of reactions undergone,
 state the conditions of the reactions,
include the structural formulae of the organic products formed.

(c) In the reaction of hexane with bromine, a mixture of monobromohexanes was formed.

(i) Draw the structural formulae of all the possible structural isomers of
monobromohexane that was formed.

(ii) Two of the monobromohexanes drawn in (c)(i) exhibit optical isomerism.

I What do you understand by the term optical isomerism?

II Draw a pair of optical isomers using either of the two monobromohexanes.

[5]
2006 AJC H2 Promos (modified)

Discussion Questions
4 One of the most common uses of alkanes is to burn them in air in the internal combustion engine.
Branched chain alkanes containing between 8 and 12 carbon atoms per molecule are preferred for
this.

(a) Draw the structural formula of

(i) the most highly-branched compound with molecular formula C8H18.

(ii) a singly-branched chiral compound with molecular formula C10H22.

[2]

(b) Write a balanced equation for the complete combustion of octane, C8H18, and hence
calculate the volume of air (at room temperature and pressure) needed to burn 100 g of
octane. [Assume air contains 20% oxygen by volume.]
[5]
[1315 dm3]
(c) Under controlled conditions, alkanes can be cracked to produce alkenes which are more
useful.

(i) What conditions are usually employed for the cracking reaction?

(ii) Suggest two different types of useful large-scale chemicals that are obtained from
alkenes.

(iii) Draw the structural formula of each of the products B and C from the following
cracking reactions.

I (CH3)2CHCH2CH2CH3  C4H8 + CH3CH3

B

II CH3CH2CH2CH(CH2CH3)2  C5H10 + CH3CH2CH3

C
[5]
N98 P1 Q7

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5 (a) What is meant by the term optical isomerism? Draw the structural formula of the alkane with
the lowest Mr that can exhibit optical isomerism.

(b) Catalytic cracking is a process whereby long-chain alkanes are broken down into mixtures of
molecules with shorter chains.

(i) Why is this process important industrially?

(ii) What conditions are used to carry out the reaction?

(iii) When the alkane C14H30 was subjected to catalytic cracking, four products with Mr:
28, 42, 44 and 56 were identified.
Suggest structural formulae for the four products and predict which one does not
decolourise aqueous bromine. Write a balanced equation for their formation from
C14H30.
J95 P1 Q9

6 C4H8 can exist in 4 non-cyclic isomers forms, W, X, Y and Z.

W has the structure as shown:

W reacts with chlorine under two different conditions.

Reaction I:
In the absence of light, W reacts with Cl2 dissolved in CCl4 to give an equimolar mixture of two
isomers A and B.
Reaction II:
W reacts with Cl2 gas under ultraviolet light to give CH 2=CH(CH2CH2Cl). However, the presence of
trace amount of nitrogen monoxide may decrease the rate of reaction.

(i) Draw the isomeric structures of X, Y and Z and identify the types of isomerism present.
[3]

(ii) Draw the displayed formulae of isomers A and B in reaction I (revisit this question after the
topic Alkenes).
[2]

(iii) Explain why the following step rarely occurs in reaction II.

CH2=CH(CH2CH3) + Cl• → CH2=CH(CH2CH2Cl) + H•

[1]

(iv) Suggest why the presence of nitrogen monoxide will slow down reaction II.
[1]
2008 MJC H2 Prelim P3 Q2(b)

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7 (a) With the crude oil prices hitting over US$200 a barrel, many motorists are opting for lower
octane rating petrol to make ends meet. The octane rating of a fuel is the knock resistance
(anti-knock rating) compared to a mixture of an isomer of octane and heptane. As octane
has a total of 18 isomers, It is useful to study how these isomers may be used to derive
cheaper but yet acceptable knock resistance fuel.

Isomers of octane may be distinguished by their optical activity (or lack of it) when they are
passed through a polarimeter.

(i) Explain what is meant by optical activity.

(ii) Two isomers of octane have the same properties except in their interactions with
plane polarised light. Draw the structures of these isomers.

(iii) Draw an isomer of octane which contains chiral carbons but is optically inactive.
[3]

(b) Isomers of octane may be distinguished by the number of mono-brominated products

formed upon reaction with bromine dissolved in tetrachloromethane under ultraviolet light.

(i) Draw an isomer of octane which reacts with limiting bromine to give
 only one mono-brominated product,
 three mono-brominated products (ignore stereoisomers).

(ii) Describe the mechanism of the reaction between octane and bromine to form 3-
bromooctane under ultraviolet light.
[5]
2008 RJC H2 Prelim P2 Q6(a) & (b)

8 Chloroalkanes and bromoalkanes can be made by the reaction of the corresponding halogen with
alkanes, for example:
CH3CH3 + Cl2  CH3CH2Cl + HCl

(i) State the conditions needed for this reaction.

(ii) Name and describe the mechanism of this reaction.

(iii) Suggest why it is not possible to make iodoalkanes by this method.

N2010/III/1c

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Section B: Multiple Choice Questions

1 As the number of carbon atoms in the homologous series of alkane molecules increases, for
which property of the alkanes does the numerical value decrease?

A density
B enthalpy change of vaporization
C number of isomers
D vapour pressure
N00/III/4

2 The complete combustion of alkanes to produce carbon dioxide and water is an important
exothermic reaction.

Which of the following graphs shows the relationship between the number of carbon atoms in the
alkane and the number of moles of oxygen gas needed for complete combustion of the alkane?

A
B
number of
moles of
oxygen gas C
D
number of carbon
1
atoms in alkane
J03/I/23

3 The process of cracking produces useful substances from crude oil. Which of the following
represents a possible reaction for cracking?

A CH3(CH2)8CH3  CH3(CH2)4CH3 + CH2=CH2

B CH3(CH2)9CH3  CH3(CH2)4CH3 + 2 CH2=CH2
C CH3(CH2)10CH3  CH3(CH2)4CH3 + 3 CH2=CH2
D CH3(CH2)11CH3  CH3(CH2)4CH3 + 4 CH2=CH2
2006 ACJC Chem Prelim P1 Q21

4 Under controlled conditions, CH3CH2CH2CH(CH2CH3)2 can be cracked to produce X and

CH3CH2CH3.

Which one of the following could be X?

A CH3CH2CH2CH=CH2
B CH3CH2CH=CHCH3
C (CH3)2C=CHCH3
D CH2=C(CH3)(CH2CH3)
2006 MJC Chem Prelim P1 Q21

5 Which compound could not be obtained from cracking a sample nonane, CH3(CH2)7CH3?

A CH3CH=CHCH=CHCH2CH2CH2CH3
B CH3CH2CH2CH2CH3
C CH3CH2CH2CH2CH2CH=CH2
D (CH3CH2CH2)3CH

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6 In the free radical substitution of 2-methylbutane with bromine, a mixture of mono-brominated
compounds were obtained.

What is the statistical ratio of the two compounds with the highest yields?

A 1:1 B 1:2
C 1:3 D 1:6
2008 NYJC H2 Chem Prelim P1 Q16

7 Mono-substituted chloroethane can be synthesized by reacting ethane with chlorine. This reaction
takes place via free radical substitution mechanism.

Which of the following statements about the mechanism of the above reaction is false?

A Excess ethane is used to ensure that majority of the product is the mono-substituted
chloroethane.
B Very small amount of butane is formed.
C The mono-substituted chloroethane is only formed in the propagation step.
D The reaction only requires a shot of uv light to initiate the reaction.
2006 SAJC Chem Prelim P1 Q26

8 Ethane reacts with chlorine gas in the presence of ultraviolet light to form a mixture of products.
Which one of the following is false regarding this reaction?

A Both initiation and propagation steps involve homolytic fission.

B Both initiation and propagation steps produce chlorine atoms.
C Both initiation and termination steps produce hydrogen chloride.
D Both propagation and termination steps involve C-Cl bond formation.
2004 MJC Chem Prelim P1 Q20

9 The molecule 24–isopropylcholestane, which has been isolated from a class of sponge, can serve
as a biomarker and has determined the first evolutionary appearances of some species.

Carbon atoms in a molecule are classified as primary, secondary, tertiary or quaternary,

depending on whether they are directly bonded to one, two, three or four other carbon atoms.

How many tertiary carbons and how many chiral carbons are there in this molecule?

tertiary carbons chiral carbons

A 9 7
B 9 8
C 10 9
D 11 9
2015/VJC/Promos/P2/15

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For each of the questions in this section, one or more of the three numbered statements 1 to 3 may be
correct.

Decide whether each of the statements is or is not correct (you may find it helpful to put a tick against
the statements that you consider to be correct).

The responses A to D should be selected on the basis of

A B C D
1, 2 and 3 are correct 1 and 2 only are correct 2 and 3 only are correct 1 only is correct

10 On the tongue, the taste buds are chiral and can distinguish one optical isomer from another.
Which of these naturally-occurring molecules have optical isomers that may be distinguished by
taste?

1 2 3

ribose menthol maleic acid

2015/IJC/Promos/P1/20

MCQ answers

1 D 2 B 3 C 4 B 5 D
6 B 7 C 8 C 9 B 10 B

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