JURONG PIONEER JUNIOR COLLEGE

2021 JC2 H2 Chemistry (9729)

Tutorial 11: Hydrocarbon: Alkanes
(Suggested Answers)

Level 1 – Self–Check Questions

1 (a) Give the IUPAC names of the following alkanes:
(i) CH2CH3 (ii) CH2CH3
CH3CH CH2 CH CH3
CH3

CH3

1 (a) (i) 1-ethyl-4-methylcyclohexane

(ii) CH2CH3
CH3CH CH2 CH CH3
CH3
Note: longest carbon chain is 6 carbons long (solid line), not 5 carbons long
(dotted line). Always look for longest, continuous carbon chain to determine
parent chain.

Hence, the IUPAC name of the compound is 2,4-dimethylhexane.

(b) Draw the displayed and skeletal formulae of the following:

(i) 3-ethyl-3-methylhexane
(ii) 2,3,4-trimethylhexane
(iii) methylcyclopentane

1 (b) (i) 3-ethyl-3-methylhexane

displayed skeletal
H
H H
C
H
H
H H C H H H

H C C C C C C H

H H C H H H
H H
H

2023 JPJC JC2 H2 Chemistry (9729) 1 Topic 11: Alkanes

 (ii) 2,3,4-trimethylhexane
H H
H C H H C H
H H H H
H C C C C C C H
H H H H H

H C H
H
(iii) methylcyclopentane
H H
H C H
H C H
H C C H
C C
H H
H H
(c) Draw the structural formulae of all the constitutional isomers of C6H14.
(c) Three types of constitutional isomerism: chain, positional, functional group
isomerism
6 carbon chain:
H H H H H H
H C C C C C C H
H H H H H H
(hexane)

5 carbon chain:
H H H H H H H H H H
H C C C C C H H C C C C C H
H CH3 H H H H H CH3 H H
(2–methylpentane) (3–methylpentane)
4 carbon chain:
H CH3 H H H H CH3 H
H C C C C H H C C C C H
H CH3 H H H CH3 H H
(2,2–dimethylbutane) (2,3–dimethylbutane)

Note:
• Displayed formulae is not required in this question part
• None of these isomers exhibits enantiomerism
• Take care of the position of the bond and bond linkages.

2023 JPJC JC2 H2 Chemistry (9729) 2 Topic 11: Alkanes

 Answers to Multiple-Choice Questions
Qn 2 3 4 5 6 7 8 9 10
Ans B C B D D B D B C

2 Carbon dioxide and water are produced in the complete combustion of alkanes.
Which line on the graph correctly represents how the number of moles of oxygen gas
needed for complete combustion of the alkane varies with the number of carbon atoms
in the alkane?

A
number of
B
moles of
oxygen gas
C

1 number of carbon atoms in alkane

Answer: B
Let the molecular formula of the straight chain alkane be CnH2n+2.
3n +1
CnH2n+2 + ( ) O2 → nCO2 + (n + 1)H2O
2
3 1
amount of O2 required = n + (i.e. y = mx + c straight line graph)
2 2

3 10 cm3 of a gaseous hydrocarbon was exploded with 100 cm3 of oxygen. The volume
of gas remaining at the end of the combustion was 75 cm3. After shaking these gases
with aqueous sodium hydroxide, the final volume of gas remaining was 25 cm3. All
volumes were measured at room temperature and pressure.
What is the molecular formula of the hydrocarbon?
A C2H4 B C2H6 C C5H10 D C5H12
Answer: C
Volume of O2 left after reaction = 25 cm3 (NaOH(aq) reacts with acidic CO2 gas only.)
Volume of O2 reacted = 100 – 25 = 75 cm3
Volume of CO2 reacted = 75 – 25 = 50 cm3
y y
CxHy + ( x + )O2 → xCO2 + H 2O
4 2
CxHy CO2 O2
Volume 10 50 75
Ratio 1 5 7.5
x=5 y
x+ = 7.5
4
y
Sub x = 5 into x + and solve:
4
y = 10

2023 JPJC JC2 H2 Chemistry (9729) 3 Topic 11: Alkanes

 4 Which statement best explains why boiling point of 2,2-dimethylpropane (9.5 °C), is
lower than that of pentane (36.1 °C)?
A The relative molecular mass of 2,2-dimethylpropane is lower than that of
pentane.
B The 2,2-dimethylpropane molecule has a smaller surface area of contact than
the pentane molecule.
C The covalent bonds in the 2,2-dimethylpropane molecule are weaker than those
in the pentane molecule.
D There are permanent dipole-dipole forces of attraction between pentane
molecules, but only instantaneous dipole-induced dipole forces of attraction
between 2,2-dimethylpropane molecules.
Answer: B
H

H H C H H
H H H H H H C C C H
H C C C C C H H H C H H
H H H H H H
pentane 2,2-dimethylpropane
Both the molecules are held together by instantaneous dipole-induced dipole attraction
(id-id). Compared to pentane, the structure of 2,2-dimethylpropane is more branched and
its electron cloud is more spherical. The id–id attraction between molecules of 2,2-
dimethylpropane is less extensive because the electron cloud has a smaller surface area
of contact. Hence 2,2-dimethylpropane has a lower boiling point.

5 N2005/P1/Q22
Why does the reaction between propane and chlorine not give a high yield of
2−chloropropane?
A A mixture of chlorine and propane cannot be prevented from exploding.
B Disubstitution by chlorine takes place preferentially to monosubstitution.
C The central carbon atom of propane is too weakly nucleophilic.
D The chlorine replaces any of the hydrogen atoms in propane.
Answer: D
Free–radical substitution is random (i.e. not selective, any of the hydrogen atoms
in the hydrocarbon can be replaced.).
Since propane has 2 types of replaceable hydrogen atoms, both
2–chloropropane and 1–chloropropane can be formed. Also, there is the possibility
of further substitution on the mono–chlorinated product to form polysubstituted
chlorinated products.
Hence, a mixture of products will be formed and the yield of 2-chloropropane
will be lowered.

2023 JPJC JC2 H2 Chemistry (9729) 4 Topic 11: Alkanes

 *6 Which of the following is a propagating step in the reaction between methane and
bromine in the presence of light?
A Br2 → 2Br•
B •CH3 + Br• → CH3Br
C •CH3 + HBr → CH3Br + H•
D •CH3 + Br2 → CH3Br + Br•
Answer: D
A: This is the initiation step.
B: This is the termination step.
C: H• will not be formed during free radical reaction.
One way to look at this is to calculate the enthalpy change of reaction for this
step to see if it is favourable:
Hrxn = E(bonds broken) − E(bonds formed)
= E(H−Br) − E(C−Br) = 366 − 280 = +86 kJ mol−1 (endothermic)
Compared this with option D:
Hrxn = E(bonds broken) − E(bonds formed)
= E(Br−Br) − E(C−Br) = 193 − 280 = −87 kJ mol−1 (exothermic)
Hence, option C will not take place since it is not energetically favourable to do
so.

*7 CH3Cl(g) undergoes free-radical substitution when mixed with Cl2 and exposed to
ultra-violet light.
Which compounds are possible products from the termination steps of this reaction?
1. HCl
2. CH2Cl2
3. CH2ClCH2Cl
4. CH3CH3
A 1 and 3 only B 2 and 3 only
C 2 and 4 only D 2, 3 and 4
Answer: B
To form molecules in the termination step, two radicals must combine.
1: H• is not formed during the reaction.
✓2: •CH2Cl and Cl• radicals are both formed during the reaction,
hence, •Cl + •CH2Cl → CH2Cl2.
✓3: •CH2Cl is formed during the reaction. Hence, 2 •CH2Cl → CH2ClCH2Cl
4: •CH3 is not formed during the reaction

2023 JPJC JC2 H2 Chemistry (9729) 5 Topic 11: Alkanes

 8 Propane when reacted with chlorine in the presence of UV light yields
1–chloropropane. When propane was reacted with iodine under the same conditions,
it was found that 1–iodopropane was not formed.
Which statement best explains this difference?
A Chlorine is a stronger oxidising agent than iodine.
B Chlorine forms radicals in the presence of UV light while iodine cannot.
C The I−I bond energy is lower than the Cl−Cl bond energy.
D The H−I bond energy is lower than the H−Cl bond energy.
Answer: D
The first propagation step in free–radical substitution involves the breaking of
C–H bond and the formation of H–X bond. The question suggests that chlorine is
more reactive than iodine in this reaction.
1st step of propagation: •
CH3CH2CH3 + X• → CH3CH2CH2 + H−X

Hr = +E(C−H) − E(H−X)

A: Since this is not a redox reaction, the oxidising strength is irrelevant.
B: Since I–I bond is weaker than Cl–Cl bond, iodine forms radicals more
readily.
C: Since I atom is larger than Cl atom, I–I bond is longer and weaker. But this
does not explain why 1-iodopropane is not formed.
✓D: The H−I bond formed in the first propagation step is weaker than C–H bond
broken, this step becomes highly endothermic and takes place less readily as
compared to when the halogen atom is Cl.

*9 N2020/P3/Q2e(i)(modified)
Compound J is an organic compound that is related to a variety of insecticides.

Compound J displays stereoisomerism.

How many stereoisomers does J have?

A 2 B 4 C 8 D 16
Answer: B
J exhibits enantiomerism and it has 2 chiral carbons. Hence, J has a total of
22 = 4 stereoisomers.

2023 JPJC JC2 H2 Chemistry (9729) 6 Topic 11: Alkanes

 *10 Abietic acid is a major component of many resins.

When it is treated with excess hydrogen with Ni catalyst, it gives a compound Z.

How many chiral centres does Z have?
A 4 B 5 C 6 D 7
Answer: C

When abietic acid react with excess hydrogen with Ni catalyst, all the C=C
double bond will be reduced to form C-C single bonds.
Structure of Z will be as follow:

*
*
*
*
*
*

Focus on intersection points of large ring structure, the total number of

chiral centre will be 6 (as indicated as * mark in the diagram above)

2023 JPJC JC2 H2 Chemistry (9729) 7 Topic 11: Alkanes

 Level 2 – Application Questions

11 A gaseous hydrocarbon contains 82.75% of carbon by mass. Its density at standard

temperature and pressure is 2.59 g dm−3.

(a) Determine the empirical and molecular formula of the hydrocarbon.

Consider 100 g of the hydrocarbon.

element C H
mass / g 82.75 17.25
amount / mol 82.75 17.25
= 6.896 = 17.25
12.0 1.0
mole ratio 1 2.50
Hence, the empirical formula of the hydrocarbon is C2H5.

(b) Draw the displayed formulae of the two possible structural isomers for the
hydrocarbon.
Method 1 to determine Mr:
Under s.t.p, one mole of gas occupies a volume of 22.7 dm3.
mass of one mole of hydrocarbon at s.t.p = 2.59 × 22.7 = 58.8 g
Mr of hydrocarbon = 58.8

Method 2 to determine Mr:

Assuming ideal gas behaviour (i.e. pV = nRT),
mRT 2.59  8.31 273
Mr = = 58.8
( )
=
pV 105  1 10−3

Let molecular formula be C2nH5n

n(2  12.0 + 5  1.0) = 58.0
n=2
Molecular formula is C4H10 .

Displayed formula of structural isomers:

4 carbon chain 3 carbon chain
H H H H H H H
H C C C C H H C C C H
H H H H H H
butane H C H
H
2–methyl propane
Note: Since the question asked for “displayed formulae”, all bonds must be
shown!

2023 JPJC JC2 H2 Chemistry (9729) 8 Topic 11: Alkanes

 *12 X, Y and Z are monobrominated compounds with the molecular formula of C5H11Br.
X exhibits stereoisomerism but Y and Z do not. X, Y and Z can be formed from pentane
by the reaction shown below:
CH3CH2CH2CH2CH3 + Br2 → X + Y + Z + HBr
The approximate ratio in which X, Y and Z are formed through bromination is 2:1:3
respectively.
(a) Explain the ratio in which X, Y and Z are formed.
Assuming that the substitution process is purely random, there are 3 types of
replaceable H atoms in pentane and hence, 3 different mono–brominated
compounds are formed.
To form X, there are 4 possible H atoms to be substituted
To form Y, there are 2 possible H atoms to be substituted.
To form Z, there are 6 possible H atoms to be substituted.
Hence, the ratio of X : Y : Z is 2 : 1 : 3 (i.e. simplest ratio of 4 : 2 : 6)

(b) Draw the structural formulae of X, Y and Z.

Structure of X Structure of Y Structure of Z
CH3C*HBrCH2CH2CH3 CH3CH2CHBrCH2CH3 BrCH2CH2CH2CH2CH3

(c) State the type of stereoisomerism exhibited by X and draw diagrams to illustrate
how X gives rise to its stereoisomerism.
Type of stereoisomerism: Enantiomerism

CH2CH2CH3 CH2CH2CH3

C C
H
H Br
Br CH3
CH3

non-superimposable mirror images

2023 JPJC JC2 H2 Chemistry (9729) 9 Topic 11: Alkanes

 *12 (d) Name and describe the mechanism for the formation of X, stating the conditions
for the formation.

Name of mechanism: Free-radical substitution

Conditions: UV light, limited Br2 / excess pentane

(✓1)*- labelling of all steps correctly

Initiation step: (✓1)* (✓2) - balanced eqn + labelling of UV
(✓3) - correct radical formed with “•” on correct C
UV (✓4) - correct balanced eqn
Br Br → 2Br• (✓2) (✓5) - correct balanced eqn
(✓6) (✓7) - for each of any 2 possible eqn for termination
UV
OR Br2 → 2Br• equations, showing clearly radical involved.

Propagation step: (✓1)*

•
Br• + CH3CH2CH2CH2CH3 → CH3CHCH2CH2CH3 + HBr (✓4)
(✓3)
•
CH3CHCH2CH2CH3 + Br2 → CH3CHBrCH2CH2CH3 + Br• (✓5)

Termination step: (✓1)*

2 Br• → Br2

•
CH3CHCH2CH2CH3 + Br• → CH3CHBrCH2CH2CH3 (✓6) (✓7)

• CH3CHCH2CH2CH3
2CH3CHCH2CH2CH3 → CH3CHCH2CH2CH3

*13 A student wanted to synthesise 2-bromo-2-methylpropane from 2-methylpropane and

bromine. He added a few drops of bromine to a sample of 2-methylpropane. No
reaction occurs when bromine is kept in the dark. However, when the sample
is exposed to sunlight, the reddish brown colour of bromine slowly decolourises
and a misty gas given off.
(a) Identify the misty gas formed.
HBr(g)

(b) Why is the short exposure to sunlight necessary for the reaction to form bromine
radicals?
UV light provides energy for homolytic cleavage of Br–Br bond to form Br•.
Once the reaction has initiated, the Br• radical is regenerated in the
propagation step and the chain reaction can continue.
Hence, a short exposure of sunlight will suffice for free radical substitution to
occur.

2023 JPJC JC2 H2 Chemistry (9729) 10 Topic 11: Alkanes

 *13 (c) State and describe the mechanism for the synthesis of
2-bromo-2-methylpropane by showing the initiation, propagation and termination
steps.
initiation step: (✓1)*
Br ⎯⎯⎯ UV → 2Br • (✓ ) (Note: If arrow is shown, it must be .)
2 2

propagation step: (✓1)*

CH3 CH3 (✓3)
CH3C CH3 + Br CH3C CH3 + HBr (✓4)
H
CH3
CH3
+ Br2 CH3C CH3 + Br (✓5)
CH3C CH3
Br

termination step: (any two equations) (✓1)*

Br + Br Br2
CH3 CH3
CH3C CH3 + Br CH3C CH3 (✓1)*- labelling of all steps correctly
(✓2) - balanced eqn + labelling of UV
(✓6) (✓7) Br (✓3) - correct radical formed with “•” on
CH3 correct C
CH3 (✓4) - correct balanced eqn
CH3C CH3 (✓5) - correct balanced eqn
2 CH3C CH3 (✓6) (✓7) - for each of any 2 possible eqn
CH3C CH3 for termination equations,
showing clearly radical involved.
CH3

(d) With the aid of appropriate equations, show how the following compounds can
be formed from the halogenation of 2-methylpropane and bromine:
(i) 2,5-dimethylhexane, (CH3)2CHCH2CH2CH(CH3)2
2–methylpropane has 2 types of replaceable H atoms. Hence, the following
alkyl radical can be formed during the reaction too.
CH3 H
CH3C C
H H
When two of this alkyl radical combine, 2,5–dimethylhexane is formed.
CH3 H CH3 H H CH3
2 CH3C C CH3C C C C CH3
H H H H H H

2023 JPJC JC2 H2 Chemistry (9729) 11 Topic 11: Alkanes

 (ii) 2,2,3,3-tetramethylbutane, (CH3)3CC(CH3)3
CH3
CH3
CH3C CH3
2 CH3C CH3
CH3C CH3
CH3

Note: For free radical substitution, alkanes with longer carbon chain can be
formed in the termination step. Usually, the number of the carbon atoms in the
alkane product formed in the termination step is a multiple of the number of
carbon atoms in the alkane reactant. Hence, when a bigger alkane molecule is
formed, you need to know where the C–C bond is formed.

(e) (i) Suggest why this method of synthesising 2-bromo-2-methylpropane by the

student is not practical.
Free–radical substitution is random (i.e. not selective).
Since 2–methylpropane has 2 types of replaceable hydrogen atoms, 2
types of monobrominated products can be formed. Also, there is the
possibility of further substitution to form polysubstituted products.
Hence, a mixture of products will be formed and the yield of
2-bromo -2-methylpropane will be lowered.

(ii) Draw the structure of the other possible product formed and state the ratio
of the two products formed.
CH3 H
CH3C C Br

The other product is H H (i.e. 1–bromo–2–methylpropane).

To form 1–bromo–2–methylpropane, there are 9 possible H atoms.
To form 2–bromo–2–methylpropane, there are 1 possible H atoms.
 1–bromo–2–methylpropane : 2–bromo–2–methylpropane is 9 : 1.

2023 JPJC JC2 H2 Chemistry (9729) 12 Topic 11: Alkanes

Level 3 – Challenging Questions

14 Light of a longer wavelength is lower in energy than light of a shorter wavelength.

Chlorine and bromine react with alkane in the presence of light.
(a) Outline the mechanism of the reaction between methane and bromine to form
bromomethane
Type of mechanism: free radical substitution

any 2 eqns

(b) Use your mechanism to explain why the bromination of methane can be carried
out with light of a longer wavelength (yellow light is adequate) than that needed
for the chlorination of methane (blue or ultraviolet light is required)
Compared to Cl–Cl bond, Br–Br bond is longer and weaker, requiring less
energy to break the bond. Hence, since light of a longer wavelength is lower in
energy, the bromination of methane can be carried out with light of longer
wavelength.

(c) Predict the relative proportions of L, M and N that are likely to be produced from
3-ethylpentane. Explain your answer.
The proportion of L : M : N is 1 : 6 : 9.
In a molecule of 3–ethylpentane, there are three types of replaceable H atoms.
Since the substitution is random, 3 different mono−brominated products are
formed
To form L, there are only 1 possible H atoms to be replaced.
To form M, there are 6 possible H atoms to be replaced.
To form N, there are 9 possible H atoms to be replaced.

(d) When the chlorination is carried out and the products are analysed, it is found that
the mole ratio of L : N formed is about 2 : 1.

2023 JPJC JC2 H2 Chemistry (9729) 13 Topic 11: Alkanes

 Suggest an explanation for the difference between this ratio and the one you gave
in (c).
The rate (or ease) of forming a tertiary radical is higher than that for primary
radical since tertiary radical is more stable due to the presence of 2 more
electron–donating alkyl group.

2023 JPJC JC2 H2 Chemistry (9729) 14 Topic 11: Alkanes