Updated 16 Dec 2014

Victoria Junior College

2015 JC2 Chemistry
Arenes: Benzene and Methylbenzene (Tutorial answers for Tutors)
H1 / H2
Summary
Reactions common to both benzene and methylbenzene
Reaction
Reagent
Condition
Type
Benzene
Cl2,
anhydrous
FeCl3

Cl

Product for
Methylbenzene
CH3

Cl

Cl

Room temp.

CH3

Electrophilic
substitution
[Substitution
for H1]

Room temp.,
CH3CH2Br,
excess
anhydrous
benzene /
AlBr3
C6H5CH3
Conc.
HNO3,
conc.
H2SO4

[H2 only]

CH3

CH2CH3

CH3

55 to 60oC for
benzene,

CH3

NO2

30oC for
methylbenzene

Reactions for methylbenzene only (side-chain reactions)

Reaction
Reagent
Condition
Reactant
Type

NO2

NO2
CH3

Products
CHBr2

CH2Br

Free radical
substitution

Br2

uv light

[Substitution
for H1]

Oxidation

CH2CH3

CH2CH3

CBr3

Methylbenzene

KMnO4(aq)
/ H2SO4 (aq)

CO2H

Reflux
1

Updated 16 Dec 2014

evels 1 and 2: Foundation and intermediate question

1 Write structural formulae for the following benzene derivatives.
(a) 2,4,6-trinitrophenol
(b) 1,4-dichlorobenzene
(c) 2-hydroxybenzoic acid
(d) 2-chlorophenylamine
Suggested solution:
(a)
OH
NO2
NO2

(b)

Cl

NO2
(c)

(d)

OH
COOH

Cl
Cl
H 2N

Describe how you would distinguish between the following pairs of compounds:
(a) Benzene and cyclohexane
(b) Benzene and cyclohexene
(c) Benzene and methylbenzene
Include clearly in your answers the reagents, conditions and observation for each
compound.
Suggested solution:
(a) Reagents: Br2, anhydrous FeBr3
Conditions: room temperature (absence of uv light)
Observation: Benzene decolorizes the reddish-brown bromine whereas
cyclohexane does not.
(b) Reagents: Br2, aqueous or dissolved in CCl4
Conditions: room temperature
Observation: Cyclohexene decolorizes the
whereas benzene does not.

reddish-brown

bromine

(c) Reagents: KMnO4(aq) / H2SO4(aq)

Conditions: heat
Observation: Methylbenzene decolorizes the purple KMnO4 and forms a
white ppt. whereas benzene does not react.
3

N98/II/5
(a) On complete combustion, 0.00754 mol of a hydrocarbon E gave 2.654 g of CO2
and 0.543 g of H2O.
2

Updated 16 Dec 2014

(i)
(ii)
(iii)
(iv)

Calculate the mass of carbon present in 1 mol of E.

Calculate the mass of hydrogen present in 1 mol of E.
Determine the molecular formula of E.
Construct an equation for the complete combustion of E.
[4]

(b) E burns with a smoky flame. 1 mol of E reacts with 1 mol of bromine molecules.
(i) Draw the displayed formula of E.
(ii) Draw the displayed formula of the product formed between E and bromine.
[2]
(c) (i)
(ii)

What organic product would you expect if E is heated under reflux with
concentrated alkaline potassium manganate (VII)?
Suggest what colour change might be observed.
[2]

Suggested solution:
(a) (i) Mass of carbon present in 1 mol of E = (2.654 12 / 44) / 0.00754
= 96.0 g
(ii)

Mass of hydrogen present in 1 mol E = (0.543 2 / 18) / 0.00754

= 8.00 g

(iii)
Moles of atoms in 1 mol of E
Molecular formula of E is C8H8.
(iv) C8H8 + 10 O2

8CO2 + 4H2O

(b) (i)

H H
C C

E
(ii)

H H
C C

Br Br
(c) (i)

C
96 / 12
=8

H
8/1 = 8

Updated 16 Dec 2014

COO K +

(ii) Decolorisation of purple KMnO4 with formation of brown ppt.

4

N2008/II/3(a)
(a) Potassium manganate (VII), KMnO4, in acidic or alkaline solution, is widely used
as an oxidizing agent in organic and inorganic chemistry.

Draw the structures of the organic compounds formed when the following
compounds are heated under reflux with concentrated alkaline KMnO4, followed
by acidification.
[3]
Suggested solution
CH3
CHCH CH2
CH3

(CH3)2CHCO2H

CH2CH2OH

CO2H

CH3

CO2H

[(b) for H2 students only]

Methylbenzene is required on a large scale as an industrially important organic
compound and also because it is added to high grade unleaded petrol / gasoline.
CH3

Methylbenzene
(a) Methylbenzene is manufactured by passing heptane, C7H16, vapour over a
catalyst. In the process, there is one gaseous by-product.
(i)

Construct an equation for this process, showing the structural formulae of

the organic molecules.
4

Updated 16 Dec 2014

(ii)

The reaction is endothermic. Explain what conditions of temperature

would favour a high equilibrium yield.

(iii) Use the equation in (a)(i) to explain what conditions of pressure would
favour a high equilibrium yield.
(iv) 1,3-dimethylbenzene can be produced by a similar process. Suggest the
structural formulae of a C8 alkane which might produce 1,3dimethylbenzene.
[7]
(b) Devise a two-step synthesis, starting with methylbenzene, of 3-nitrobenzoic
acid. Identify the reagents at each step, and draw the structural formula of the
intermediate.
[2]
Suggested solution
(a) (i)

CH3

CH3(CH2)5CH3
(ii)

4 H2

High temperature gives a high yield. By Le Chateliers Principle, the

forward endothermic reaction is favoured as it removes the excess
heat.

(iii) Low pressure gives a high yield. By Le Chateliers Principle, the

forward reaction is favoured as it results in more moles of gases and
hence increases the pressure of the system.
(iv)

OR

OR

[Explanation
5

Updated 16 Dec 2014

Consider the following 6-carbon chain in which C1 joins to C6 to

form the benzene ring:

Since the 2 methyl groups in 1, 3dimethylbenzene are two carbon

atoms apart, they can be attached to either (i) C1 and C3, (ii) C2 and
C4 or (iii) C1 and C5]
(b)

N.B: Sequence of steps cannot be changed since CH3 is o, p-directing.

Conditions not asked for in the question.
H2 only
6 N92/IV/22
The reaction between boiling methylbenzene and chlorine takes place in a number
of steps to give several products. Which of the following could be one of the steps?
CHCl2

CHCl

CH2Cl

CH2

CH2Cl

Cl

CH3
D

HCl

CH2+
C

+ Cl

Cl2

CH3

+
H

Cl

H+

Cl

Updated 16 Dec 2014

CH3

CH3

Cl+

+
H
Cl

Answer: A
Level 3: Challenging question
7 (a) When beryllium and carbon are heated strongly in the absence of air, a solid
product A can be extracted. A reacts with water to produce a gaseous
hydrocarbon B which contains 75% of carbon by mass.
(i)

Suggest formulae for A and B.

(ii)

Hence write a balanced equation for the reaction of A with water.

(b) Consider the following reaction, in which a compound of beryllium, BeCl2, acts
as a Lewis acid catalyst to generate a reactive electrophile:

(i)

With reference to the electronic structure, explain why BeCl2, can be used
as a Lewis acid catalyst in the above reaction.

(ii)

Describe the mechanism of the reaction, showing clearly the catalytic role
of BeCl2. You should include curly arrows indicating the movement of
electrons, and all charges in your answer.

Suggested solution
(a) (i) Since A is formed from Be and C in the absence of air, A contains
only these two elements. A must have the formula Be2C.

Since B is a hydrocarbon, it contains only carbon and hydrogen.

C
75
75 / 12 = 6.25
1

Mass %
Relative no. of moles
Simplest ratio
Hence, B is CH4.
7

H
25
25 / 1 = 25
4

Updated 16 Dec 2014

(ii)

(b) (i)

Be2C + 4H2O
[Be2C + 2H2O

2Be(OH)2 + CH4
2BeO + CH4 also acceptable]

Be atom is 4 electrons short of an octet in BeCl2. It thus has empty p

orbitals to accept a lone pair of electrons, enabling it to act as a
Lewis acid.

(ii)
H

+
H
+

CH3+

CH3

+ AlCl4-

CH3

CH3

AlCl3

Methylbenzene

HCl

Updated 16 Dec 2014

Step 3: Formation of product

O

O
H

BeCl 3-

BeCl 2

HCl

OR
O

O
H

BeCl 42-

BeCl 2

+ 2 HCl

BeCl2, being a catalyst, is regenerated in the final step.

Supplementary questio
1 N98/III/22
Which compound can be obtained by reacting a hydrocarbon with bromine in the
presence of a halogen carrier?
CH2Br
A

CH2

CHCH2Br

CH2CH3
B

CH3CHBrCH3

Br
2

N99/III/23 [H2 only]

What is the correct set of conditions for the conversion of benzene into
nitrobenzene?

A
B
C
D

Acid
Dilute HNO3
Concentrated HNO3
Concentrated HNO3
and concentrated
H2SO4
Concentrated HNO3
and concentrated

temperature
100oC
0OC
10oC
120oC
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Updated 16 Dec 2014

H2SO4
Explanation: 10oC is the starting temperature rather than the actual
temperature required for nitration. As nitration is highly exothermic, it is
necessary to start with a low temperature, thus allowing the heat evolved by
the reaction to gradually raise the temperature to the required level.
3

J01/III/21
Which property does benzene have as a consequence of the delocalisation of
electrons in the benzene molecule?
A
B
C
D

Benzene is a good conductor of electricity.

The carbon-carbon bond lengths are between those of CC bonds and C=C
bonds.
Addition reactions of benzene take place more easily than substitution.
Substitution in benzene takes place at one particular carbon atom.

[New update: H1 students, please note that this qn is for H2 only]

During the nitration of benzene, a nitro group substitutes at a carbon atom.
What is the arrangement of the bonds at this carbon atom during the reaction?

A
B
C
D
5

at the start of the

reaction

in the intermediate
complex

at the end of the

reaction

planar
planar
planar
tetrahedral

Planar
tetrahedral
tetrahedral
tetrahedral

Planar
Planar
Tetrahedral
Tetrahedral

[H2 only]
Which statement is true regarding the formation of chlorobenzene from benzene
and chlorine?
A
B
C
D

A catalyst is not required for the reaction to take place.

The six carbon atoms in benzene remain sp2 hybridised throughout the reaction.
The relative molecular mass of the organic product is 35.5 greater than that of
benzene.
The reaction involves an intermediate which contains 4 delocalized electrons.

Explanation:
A: A Lewis catalyst, e.g. FeCl3, is required to generate a strong electrophile,
Cl+.
B: The structure of the intermediate is:

10

Updated 16 Dec 2014

Cl
H

*
+
The reactive C (marked with *) has changed from being sp2 hybridized in
benzene to sp3 hybridized in the intermediate. Hence, only 5 carbon atoms
remain sp2 hybridised throughout the reaction.
C: One H atom has been replaced by one Cl atom. Hence the Mr changes by
35.5 1 = 34.5.
D: Since the intermediate has a positive charge, only 4 delocalized pi
electrons are shared among the 5 carbon atoms other than the reactive atom.

Which of the following about methylbenzene and its derivatives are correct?
1
2
3

There are four aromatic isomers of molecular formula C7H7Cl.

Methylbenzene reacts with warm acidified potassium dichromate (VI) solution.
Methylbenzene is a planar molecule.

Explanation:
1: The four isomers are

2: Potassium dichromate (VI) is a weaker oxidizing agent than potassium

manganite (VII).
Hence, methylbenzene is not oxidized by potassium
dichromate (VI).
3: The methyl C is sp3 hybridized and hence has a tetrahedral arrangement.
Methylbenzene is thus non-planar.
7

N97/I/6
Methylbenzene can be used as an additive in unleaded petrol. Some chemical
transformations of methylbenzene are given below.
11

Updated 16 Dec 2014

CO2H

I
CH3

II

CH2Br

III
CH3
Br
A
(a) Suggest reagents and conditions for each of the reactions I, II and III, and
[8]
describe as fully as you can the type of reaction undergone in each case.
(b) There are two other positional isomers of A. Draw their structural formulae, and
suggest which one is more likely to be formed along with A in reaction III.
[2]

Suggested solution:
(a)
Reaction Reagents
I
KMnO4(aq) /
H2SO4(aq)
II
Br2

III

Conditions
Reflux

Reaction type
Oxidation

uv light,
excess
methylbenzene

Free radical
substitution [H2]

Br2,
Room
anhydrous FeBr3 temperature

Substitution [H1]
Electrophilic
substitution [H2]
Substitution [H1]

(b) The two isomers are

CH3

Br

CH3

Br
B

Isomer C is more likely to be formed.

8

[parts (b) and (c) for H2 only]

(a) (i) By using relevant data from the Data Booklet, calculate the enthalpy change
for the hydrogenation of cyclohexene.
12

Updated 16 Dec 2014

(ii) In 1865, Friedrich Kekule described benzene as a ring of alternating single

and double bonds:

From experimental determination, the enthalpy change of hydrogenation of

benzene was found to be -205 kJ mol-1.
Explain, in terms of the structure of benzene, why this value is not three
times your answer in (a)(i). Use an energy level diagram to illustrate your
answer.
[3]
(b) Nitrobenzene is prepared by reacting benzene with a nitrating mixture.
(i)Describe the mechanism for the formation of nitrobenzene from benzene.
(ii) During the nitration reaction, a di-substituted product is also formed. Draw
the likely structure of this product.
[4]
(c) Iodine monochloride, ICl, can be prepared by passing chlorine gas over iodine
crystals and it is collected as a dark brown liquid.
Draw the structure of the likely organic product of the reaction of ICl with
methylbenzene in the box below:

[1]

Suggested solution:
(a) (i) The overall process involves breaking a C=C and a HH bond and
forming a CC bond and 2 CH bonds.
Hence, H = 610 + 436 [350 + 2(410)]
= -124 kJ mol-1

13

Updated 16 Dec 2014

(ii) Since the structure proposed by Kekule has 3 C=C, its enthalpy
change of hydrogenation of the structure should correspond to three
times the answer in (a)(i).
By representing the enthalpy change of hydrogenation of Kekule
structure and benzene on the energy level diagram below,
Enthalpy /
kJ mol-1

+ 3H2(g)
(l) + 3H2(g)
-372
-205
(l)

it can be seen that benzene has a lower energy content than the
Kekule structure. This is because benzene has been stabilized by
resonance which is brought about by delocalization of the pi electrons
around the ring.
(b) (i) Reaction type: electrophilic substitution
The electron-rich benzene ring is attacked by the electrophile, NO2+
H
NO2

NO2+

The intermediate loses a proton to HSO4- and the H2SO4 catalyst is

regenerated.
NO2
H
NO2
+ H2SO4
+ HSO4
+

(ii)

14

Updated 16 Dec 2014

(c)

[Explanation: I, being less less electronegative than Cl, will have the +
charge in ICl. Hence, I+ acts as the electrophile which attacks the
benzene ring.]

Refer to Ten-Year Series Topic 10.2: Hydrocarbons for the questions below:
Section A
Question
Q1 [N04/I/21]
Q5 [N06/I/22]

Answer
D
A

Paper3
Q4(c) N06/III/8(c) [H2 only]
Suggested solution
(c) (i) An electrophile is an electron pair acceptor. It lacks electrons and
hence is attracted to electron-rich regions.
(ii)

Cl+ + AlCl4- [FeCl3 can also be used instead of AlCl3.]

Cl2 + AlCl3
Aluminium chloride is a Lewis acid which accepts a lone pair from a
chlorine atom, thereby forming Cl+ and AlCl4-.

(iii)
CH3

CH3

Cl+
H

Cl

[OR show mechanism with electrophile at ortho position.]

15

Updated 16 Dec 2014

CH3

CH3
+
H

Cl

+ AlCl4-

+
Cl

16

AlCl3 + HCl