[3]

HALOGENOALKANES WS 1
16

[Total : 11]

Chlorofluorocarbons, CFCs, are small alkane molecules in which some of the hydrogen
atoms have been replaced by atoms of chlorine and fluorine.
(a) (i)

State two uses of CFCs.

...................................................................................................................................
...................................................................................................................................

(ii)

What property of CFCs causes them to be useful?

...................................................................................................................................
[2]

(b) A typical CFC is CHF2CHClF.

(i)

Which covalent bond in this CFC is the weakest?

...................................................................................................................................

(ii)

Why does this CFC present an environmental concern?

11
...................................................................................................................................
(c) Another
CFC contains the following elements by mass. The value of its M r is 135.
...................................................................................................................................

For
Examiners
Use

C, 17.8%;
H, 1.5%;
Cl , 52.6%;
F, 28.1%
...................................................................................................................................
Use these
data to determine the molecular formula of the CFC.
...................................................................................................................................
[3]
11
9701/2/M/J/02

(c) Another CFC contains the following elements by mass. The value of its M r is 135.
C, 17.8%;

H, 1.5%;

Cl , 52.6%;

F, 28.1%

Use these data to determine the molecular formula of the CFC.

[3]
[Total : 8]

[3]
[Total : 8]
Bilal Hameed

For
Examiners
Use

10

25

For
Examiners
Use

CH3
CH3

Br

CH3CH2CH2CH2Br

CH3

1-bromobutane

2-bromo-2-methylpropane

(a) 1-Bromobutane reacts with aqueous sodium hydroxide to form butan-1-ol.

(i)

Give a balanced equation for this reaction.

...................................................................................................................................

(ii)

Name the type of reaction. ........................................................................................

(iii)

Describe the mechanism of this reaction.

[5]
(b) 1-Bromobutane and 2-bromo-2-methylpropane both react with an ethanolic (alcoholic)
solution of sodium hydroxide to form alkenes.
(i)

Name the type of reaction. ........................................................................................

(ii)

Identify, by means of the structural formula, the alkene formed from

I 1-bromobutane,

II 2-bromo-2-methylpropane.

9701/02/O/N/03

Bilal Hameed

11
(iii)

Hot, concentrated manganate(VII) ions break the double bond in alkenes. Each of
the two alkenes in (b)(ii) gives CO2 and H2O from the terminal group, but the rest
of the molecule remains as an organic oxidation product. Suggest the formula of
each of these products.
from I .........................................................................................................................
from II ........................................................................................................................
[5]

(c) Complete the reaction sequence giving the intermediate, the reagents and the
conditions for the synthesis of 2,2-dimethylpropanoic acid.

CH3
CH3

CH3
Br

step

step

II

CH3

Step I:

CH3

CO2H

CH3

reagent .............................................................................................................
conditions .........................................................................................................

Step II:

reagent .............................................................................................................
conditions .........................................................................................................
[3]
[Total : 13]

9701/02/O/N/03

Bilal Hameed

For
Examiners
Use

[Total : 11]

35

A number of organic compounds containing the halogens fluorine and/or chlorine are
commercially important because of their chemical inertness.
(a) Name three such compounds, and for each state a use where its inertness is important.
(i)

...................................................................................................................................
...................................................................................................................................

(ii)

...................................................................................................................................
...................................................................................................................................

(iii)

...................................................................................................................................
...............................................................................................................................[6]

(b) Under certain conditions in the upper atmosphere, some of these compounds break
down.
(i)

Explain how this happens and what effects this has, in chemical terms.
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................

(ii)

Suggest alternative compounds, which do not contain a halogen, for two of the
uses you have given in (a).
...................................................................................................................................
...............................................................................................................................[5]
[Total : 11]

UCLES 2004

Bilal Hameed

9701/02/M/J/04

44

Compound G, in which R represents the rest of the molecule, was made for use as a tear
gas in World War 2.
H
R

CN

Br
compound G
Compound G was made by the following sequence of reactions.
RCH3
(a)

stage I

RCH2Cl

stage II

RCH2CN

stage III

RCHBrCN

(i) For stage I and for stage II, state the reagent(s) and condition(s) used to carry out
each change.
stage I

reagent(s) ..................................................................................................
condition(s) ................................................................................................

stage II reagent(s) ..................................................................................................

condition(s) ................................................................................................
(ii) Suggest the reagent(s) and condition(s) necessary to carry out stage III.
reagent(s) .................................................................................................................
condition(s) ...............................................................................................................
[6]

UCLES 2005

Bilal Hameed

9701/02/M/J/05

For
Examiners
Use

9
Compound G was not actually used in World War 2 and stocks of it had to be destroyed
safely. The following sequence of reactions was used in this process.
RCHBrCN

stage IV

RCHBrCO2H

stage V

RCH(OH)CO2H
stage VI
RCH2CO2H

(b) For stage IV and for stage V state the reagent(s) and condition(s) necessary to bring
about each reaction.
stage IV reagent(s) .........................................................................................................
condition(s) ......................................................................................................
stage V reagent(s) .........................................................................................................
condition(s) ................................................................................................ [4]
(c) The full sequence of stages I to VI involves some compounds which contain chiral
centres.
(i) Explain what is meant by the term chiral centre.
..................................................................................................................................
..................................................................................................................................
(ii) Draw displayed formulae for the isomers of one compound in the full sequence of
stages I to VI which you consider to be chiral.

[3]
[Total: 13]

UCLES 2005

Bilal Hameed

9701/02/M/J/05

[Turn over

For
Examiners
Use

10

55

Many organic reactions are substitution reactions in which the number of carbon atoms in
the organic compound is unchanged.
(a) What is meant by the term substitution reaction?
..........................................................................................................................................
......................................................................................................................................[1]
(b) One example of a substitution reaction is the formation of an alcohol from a
halogenoalkane.
(i)

Write a balanced equation for the formation of ethanol from bromoethane.

..................................................................................................................................

(ii)

State the conditions for this reaction.

..............................................................................................................................[2]

(c) In a few organic reactions, the product contains one more carbon atom than the starting
material.
(i)

Write the equation for a reaction in which the organic compound bromoethane,
which contains two carbon atoms, is converted into an organic compound which
contains three carbon atoms.
..................................................................................................................................

(ii)

State the conditions for this reaction.

..............................................................................................................................[2]

UCLES 2006

Bilal Hameed

9701/02/M/J/06

For
Examiners
Use

11
(d) Ethanol may be converted into propanoic acid in a three-stage process which uses ethanol
as the only organic compound.
C2H5OH
(i)

step I

step II

step III

C2H5CO2H

Give the structural formulae of the intermediate compounds K and L.

K ...............................................................................................................................
L ...............................................................................................................................

(ii)

State the reagent(s) used and give the essential condition(s) for step I and for
step III.
step I
reagent(s) .................................................................................................................
condition(s) ...............................................................................................................
step III
reagent(s) .................................................................................................................
condition(s) ................................................................................................................
[6]
[Total: 11]

9701/02/M/J/06

Bilal Hameed

8 8

64

Complete
the the
following
reaction
scheme
which
starts
with
propene.
4(a) (a)
Complete
following
reaction
scheme
which
starts
with
propene.
In each
empty
box,
write
the
structural
formula
of
the
organic
compound
In each empty box, write the structural formula of the organic
compoundthat
thatwould
would
be formed.
be formed.

Br2Br2

CHCH
3CH=CH
3CH=CH
2 2

ForFor
Examiners
Examiners
Use
Use

+ +
KMnO
KMnO
4 /H
4 /H

cold,
dilute
cold,
dilute

A A

BB

HBr
HBr

KCN in
KCN in
aqueous
aqueous
ethanol
ethanol

NH
NH3 3
in an excess
in an excess

H2SO4(aq)
H2SO
4(aq)
heat
under
heat under
reflux
reflux

(b) Under suitable conditions, compound E will react with compound B.

(i)

NaOH(in ethanol)
NaOH(in
heatethanol)
under
heat under
reflux
reflux

[7]
[7]
For
Examiners
Use

What functional group is produced in this reaction?

............................................................

(ii)

How is this reaction carried out in a school or college laboratory?

..................................................................................................................................
..................................................................................................................................
[3]

UCLES 2010

UCLES 2010

Bilal Hameed

9701/21/M/J/10

9701/21/M/J/10

[Total: 10]

74

Halogenoalkanes have many chemical uses, particularly as intermediates in organic

reactions.
Three reactions of 1-bromobutane, CH3CH2CH2CH2Br, are shown below.
CH3CH2CH2CH2OH

CH3CH2CH2CH2NH2

reaction 1

reaction 2

CH3CH2CH2CH2Br
reaction 3

CH3CH2CH=CH2
(a) For each reaction, state the reagent and solvent used.
reaction 1

reagent ............................................................
solvent .............................................................

reaction 2

reagent ............................................................
solvent .............................................................

reaction 3

reagent ............................................................
solvent .............................................................

[6]

(b) When 1-iodobutane, CH3CH2CH2CH2I, is reacted under the same conditions as those
used in reaction 1, butan-1-ol is formed.
What difference, if any, would there be in the rate of this reaction compared to the
reaction of 1-bromobutane?
Use appropriate data from the Data Booklet to explain your answer.
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
...................................................................................................................................... [3]

UCLES 2010

Bilal Hameed

9701/21/O/N/10

For
Examiners
Use

9
Dichlorodifluoromethane, CCl2F2, is an example of a chlorofluorocarbon (CFC) that was
formerly used as an aerosol propellant. In September 2007, at the Montreal summit,
approximately 200 countries agreed to phase out the use of CFCs by 2020.

For
Examiners
Use

(c) State two properties of CFCs that made them suitable as aerosol propellants.
1. .......................................................................................
2. .......................................................................................

[2]

(d) When CFCs are present in the upper atmosphere, homolytic fission takes place in the
presence of ultraviolet light.
(i)

What is meant by the term homolytic fission?

..................................................................................................................................
..................................................................................................................................

(ii)

Suggest an equation for the homolytic fission of CCl2F2.

.............................................................................................................................. [2]

(e) The most common replacements for CFCs as aerosol propellants are hydrocarbons
such as propane and butane.
Suggest one disadvantage of these compounds as aerosol propellants.
...................................................................................................................................... [1]
[Total: 14]

UCLES 2010

Bilal Hameed

9701/21/O/N/10

[Turn over

84

Although few halogenoalkanes exist naturally, such compounds are important as

intermediates in organic reactions and as solvents.
The bromoalkane B has the following composition by mass: C, 29.3%; H, 5.7%; Br, 65.0%.
The relative molecular mass of B is 123.
(a) Calculate the molecular formula of B.

[3]
Halogenoalkanes such as bromoethane, C2H5Br, have two different reactions with sodium
hydroxide, NaOH, depending on the conditions used.
(b) (i)

When hot aqueous NaOH is used, the C2H5Br is hydrolysed to ethanol, C2H5OH.
Describe the mechanism of this reaction. In your answer, show any relevant
charges, dipoles, lone pairs of electrons and movement of electron pairs by curly
arrows.

UCLES 2010

Bilal Hameed

9701/23/O/N/10

For
Examiners
Use

9
(ii)

What will be formed when C2H5Br is reacted with NaOH under different
conditions?

For
Examiners
Use

..................................................................................................................................
(iii)

What are the conditions used?

..................................................................................................................................

(iv)

What type of reaction is this?

.............................................................................................................................. [7]

When 1,4-dichlorobutane, ClCH2CH2CH2CH2Cl, is reacted with NaOH, two different

reactions can occur, depending on the conditions used.
(c) (i)

Draw the displayed formula of the product formed when 1,4-dichlorobutane is

reacted with hot aqueous NaOH as in (b)(i).

(ii)

Draw the skeletal formula of the product formed when 1,4-dichlorobutane is reacted
with NaOH in the way you have described in (b)(ii) and (b)(iii).

[2]
[Total: 12]

UCLES 2010

Bilal Hameed

9701/23/O/N/10

[Turn over

92

Halogenoalkanes have been widely used as aerosol propellants, refrigerants and solvents
for many years.
Fluoroethane, CH3CH2F, has been used as a refrigerant. It may be made by reacting ethene
with hydrogen fluoride.
You are to calculate a value for the CF bond energy in fluoroethane.
(a) Use relevant bond energies from the Data Booklet, and the equation below to calculate
a value for the bond energy of the CF bond.
CH2 = CH2(g)

HF(g)

CH3CH2F(g)

H o = 73 kJ mol1

CF bond energy = .................................... kJ mol1 [4]

(b) Another halogenoalkane which was used as a refrigerant, and also as an aerosol
propellant, is dichlorodifluoromethane, CCl2F2.
State two reasons why compounds such as CH3CH2F and CCl2F2 have been used as
aerosol propellants and refrigerants.
..........................................................................................................................................
..................................................................................................................................... [2]

UCLES 2011

Bilal Hameed

9701/22/M/J/11

For
Examiners
Use

5
CCl2F2 is one of many chlorofluorocarbon compounds responsible for damage to the ozone
layer in the stratosphere.

For
Examiners
Use

(c) By using relevant data from the Data Booklet, and your answer to (a) suggest why CCl2F2
is responsible for damage to the ozone layer in the stratosphere whereas CH3CH2F is
not.
..........................................................................................................................................
..........................................................................................................................................
..................................................................................................................................... [2]
Both CH3CH2F and CCl2F2 are greenhouse gases.
The enhanced greenhouse effect is of great concern to the international community.
(d) (i)

What is meant by the term enhanced greenhouse effect?

..................................................................................................................................
..................................................................................................................................
..................................................................................................................................

(ii)

Water vapour is the most abundant greenhouse gas.

What is the second most abundant greenhouse gas?
........................................

[3]

A greenhouse gas which is present in very small amounts in the atmosphere is sulfur
hexafluoride, SF6, which is used in high voltage electrical switchgear.
(e) What shape is the SF6 molecule?
...................................................

[1]
[Total: 12]

UCLES 2011

Bilal Hameed

9701/22/M/J/11

[Turn over