National Junior College SH2 H2 Chemistry 2022

6 Halogen Derivatives Tutorial

Reactions of Halogen Derivatives
1 Which is a nucleophilic substitution reaction?
A

2 Which compound gives the largest number of isomeric products on reacting with hot ethanolic
potassium hydroxide?
A (CH3)3CCH2Cl
B CH3CH2CHClCH3
C (CH3)2CHCH(CH3)CH2Cl
D (CH3CH2) 2CHCH(CH3)Cl

3 Concentrated ammonia was heated in a sealed tube with excess bromoethane, C 2H5Br. Which
product will not be formed?
A C2H7N B C5H13N C C6H15N D C8H20NBr

4 [N2010/I/24] The diagram below shows a reaction synthetic pathway.

What could the product Q be?

A B C D

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National Junior College SH2 H2 Chemistry 2022

5 Chloroethane can be formed from bromoethane in two steps.

Which statements about these steps are correct?

1 Step 1 involves a nucleophilic substitution.
2 Hot aqueous sodium hydroxide is the reagent in step 1.
3 Hot aqueous sodium chloride is the reagent in step 2.

A 1 only B 1 and 2
C 2 and 3 D 1, 2 and 3

6 Suggest the synthetic routes for each of the following. Clearly indicate the reagents and conditions
for each step in your reaction scheme, and show the structure of all intermediate compounds.
(a) propane  propan-1-ol
(b) propene  2-methylpropanoic acid
(c) but-1-ene  ethanoic acid
(d) 1-bromobutane  butan-2-ol
(e) BrCH2CH2Br  HO2CCH2CH2CO2H
(f) CH3CHBrCH3 CH3CH(CH3)CH2NH2

Mechanism : Nucleophilic Substitution

7 (a) Draw a mechanism for the reaction between chloroethane and excess ammonia to form
CH3CH2NH2 and other products. Show relevant lone pairs and dipoles, and use curly arrows to
indicate the movement of electrons. [2015 P2Q2b(i)]
(b) In reaction (a) above, a by-product with molecular formula C8H20NCl is formed. It gives an
immediate precipitate with aqueous silver nitrate. Suggest a structure for this compound.
(c) State and explain how the rate of this reaction would change when chloroethane is replaced
by bromoethane.

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National Junior College SH2 H2 Chemistry 2022

8 [Modified from N96/I/8] 2bromobutane can react with hydroxide ions under two different sets of
reaction conditions to give two different product mixtures. Product C is a racemic mixture.

(a) Describe the reagents and conditions necessary for each of the reactions I and II.
(b) Describe the mechanism which CH3CHBrCH2CH3 has undergone to give product C. In your
answer, show any relevant charges, dipoles or lone pairs of electrons you consider important
in this mechanism.
(c) Product C is a racemic mixture.
(i) Explain the term “racemic mixture” and draw suitable diagrams to illustrate the
stereoisomerism exhibited.
(ii) With reference to the mechanism drawn in (b)(i), explain how a racemic mixture is
formed.
(iii) Hence, explain why product C is optically inactive even though it has a chiral carbon
centre.
(d) Product D is a mixture of three isomers, all of which decolourise bromine water. Draw the
displayed formulae of these isomers and state the type of isomerism between each suitable
pair.

9 Ethers are cleaved by HI via an SN2 mechanism.

O HI OH I
+

Which of the following is the most likely product for the following reaction?
O
2 mol HI

A O B I HO

I OH OH I

C I HO D HO I

I OH I OH

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National Junior College SH2 H2 Chemistry 2022

Distinguishing Test
10 Suggest one simple chemical test that would enable you to distinguish the following pairs of
compounds. State clearly how each compound behaves in the test. Write balanced equation(s) for
the reactions involved.
(a) CH3CH2CH2Cl and CH3CH=CH2
(b)

Relative rates of nucleophilic substitution

11 [N2009/I/23 (Modified)] When a halogen compound S was boiled under reflux with ethanolic silver
nitrate for some time, little or no precipitate was seen.
Which formula could represent S?
A CH3CH2CHClCH2CH3 B C D

12 (a) Same amount of the following five organic halogen compounds were boiled with ethanolic
silver nitrate solution. The observation with each compound is given below.
Compound Observations
2-iodobutane precipitate formed almost immediately
2-bromobutane precipitate formed after 2 minutes
2-chlorobutane precipitate slowly formed after 10 minutes
2-fluorobutane no precipitate formed
chlorobenzene no precipitate formed

(i) With the use of relevant data from the Data Booklet, explain why
 2-iodobutane, 2-bromobutane and 2-chlorobutane form precipitate at different rates,
 2-fluorobutane does not form precipitate
(ii) Explain why chlorobenzene does not form precipitate while 2-chlorobutane form precipitate
after 10 minutes.

(b) When a sample of 2-bromobut-2-ene is boiled under reflux for some time with aqueous
sodium hydroxide, cooled, acidified with dilute nitric acid and then treated with silver nitrate
solution, there is no precipitate formed. Explain the observation.

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National Junior College SH2 H2 Chemistry 2022

Halgenoalkanes and the environment

13 It has been estimated that for every chlorine atom generated from chlorofluoroalkanes in the
stratosphere, one hundred thousand molecules of ozone may be destroyed.
Which statement about chlorine atoms gives an explanation of this?
A They achieve high activation energies by absorbing ultraviolet radiation.
B They are regenerated in a chain-propagation reaction with ozone.
C They remove oxygen from the ozone-oxygen equilibrium.
D They initiate the ionisation of oxygen molecules.

14 Ozone depletion potential (ODP) is a measure of the effectiveness of chlorofluoroalkanes in

destroying stratospheric ozone.
In which sequence are compounds listed in increasing order of their ODPs?
A CHClF2 < CH3CCl2F < CCl2FCClF2
B CHClF2 < CCl2FCClF2 < CH3CCl2F
C CCl2FCClF2 < CHClF2 < CH3CCl2F
D CH3CCl2F < CCl2FCClF2 < CHClF2

15 Ozone, O3, is produced in the upper atmosphere by sunlight. The reactions are:
light
O2 O+O
O + O2 O3
Large amounts of the compound CFCl3 have been used in industry and have been released into
the atmosphere. The compound survives unchanged in the environment for approximately
75 years.
It is believed to be destroying stratospheric ozone by the following mechanism:
CFCl3 Cl• + •CFCl2 Step 1
Cl• + O3 ClO• + O2 Step 2
The chlorine atoms are then regenerated by the reaction:
•ClO + O Cl• + O2 Step 3

(a) CFCl3 was once used as refrigerant fluids in air-conditioner. Suggest two reasons why it was
suitable for this use.
(b) Suggest how the reaction in step 1 is brought about.
(c) Suggest and explain which steps would constitute the propagation stage of this reaction?
(d) Suggest two possible termination reactions.
(e) Where does the oxygen atom (O) in Step 3 come from?
(f) State the potential harm that can be caused by the effect of CFCl3 on stratospheric ozone.

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National Junior College SH2 H2 Chemistry 2022

Application questions
16 An optically active sample of 2chlorobutane reacts with ethanolic sodium cyanide to yield an
optically pure product, X.
(a) (i) Draw the full structural formula of X.
(ii) Describe the mechanism which 2chlorobutane has undergone to give X.
In your answer, show any relevant charges, dipoles or lone pairs of electrons you
consider important in this mechanism.

(b) Suggest a synthetic route for the formation of 2-methylbutanoic acid from 1-chlorobutane.
For all the steps in the reaction scheme, state the following.
(i) reagents and conditions
(ii) intermediates products

17 An optically active compound R as shown below, was heated under reflux with NaOH(aq), and two
products were formed, major product P, C10H12O, and minor product Q, C10H10. Both products P
and Q do not rotate plane-polarised light.

(a) Suggest the structures for P and Q.

(b) Describe the mechanism which R has undergone to give product P. In your answer, show any
relevant charges, dipoles or lone pairs of electrons you consider important in this mechanism.
Hence, explain why product P does not rotate the plane-polarised light after the reaction even
though it contains a chiral carbon centre.
(c) Suggest the type of reaction R has undergone to form product Q.

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