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MINISTRY OF EDUCATION, SINGAPORE

in collaboration with
UNIVERSITY OF CAMBRIDGE LOCAL EXAMINATIONS SYNDICATE
General Certificate of Education Advanced Level
Higher 2

CHEMISTRY

9647/03

Paper 3 Free Response

October/November 2010
2 hours

Candidates answer on separate paper.

Additional Materials:

Answer Paper
Data Booklet

READ THESE INSTRUCTIONS FIRST

Write your Centre number, index number and name on all the work you hand in .
Write in dark blue or black pen on both sides of the paper.
You may use a soft pencil for any diagrams, graphs or rough working.
Do not use staples, paper clips, highlighters, glue or correction fluid .
Answer any four questions.
A Data Booklet is provided.
You are reminded of the need for good English and clear presentation in your answers.
The number of marks is given in brackets [ ] at the end of each question or part question.
At the end of the examination , fasten all your work securely together.

This document consists of 10 printed pages and 2 blank pages.

;:::a~

~.l{\

Singapore Examinations and Assessment Board

UCLES & MOE 2010

UNIVERSITY of CAMBRIDGE

International Examinations
DC (N F/SHW) 33440

[Turn over

2
Answer any four questions.

(a) (i)

(ii)

Explain what is meant by the term entropy of a chemical system.

Describe and explain how the entropy of each of the following systems will change during
the stated process. Assume the pressure of each system remains at 1 atm throughout.

1 mol of CZ 2 (g) at 298 K is added to 1 mol of N2 (g) at 298 K.

1 mol of CZ 2 (g) at 298 K is heated to 373 K.

1 mol of CZ 2 (g) at 298 K is reacted with iodine according to the following

equation.
CZ 2 (g) +

1/ 1 (s)
3 2

--7

2/
3

ICZ 3 (1)

1 mol of CZ 2 (g) at 1000 K is photolysed according to the following equation.

CZ 2 (g) --7 2CZ(g)

[5]

(b) (i)

Describe how the reaction of hydrogen with chlorine differs from that of hydrogen with
bromine.

(ii)

How would you expect the reaction of hydrogen with fluorine to differ from that of hydrogen
with chlorine?

[2]
(c) Chloroalkanes and bromoalkanes can be made by the reaction of the corresponding halogen
with alkanes, for example:

(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.

[6]

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(d) Suggest a structural formula for each of the compounds A - 0 in the following schemes.

NaOH in ethanol
heat

..

\~------~y~------~}

a mixture of these two products formed

NaOH in ethanol
heat

..

only one product formed

Br2 (in an inert solvent)

..

NaOH in ethanol
heat

..

only one product formed

[4]
(e) Chlorofluoroalkanes, CFCs, were once used as refrigerant fluids and aerosol propellants. In
many applications they have now been replaced by alkanes. This is because CFCs contribute
to the destruction of the ozone layer.
(i)
(ii)
(iii)

Suggest one reason why CFCs were originally used for these purposes.
Explain how CFCs destroy the ozone layer.
Suggest one potential hazard of using alkanes instead of CFCs.

[3]
[Total : 20]

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The soy bean, Glycine max, is a legume native to East Asia. It was first cultivated in China over
5000 years ago.
The beans have many culinary uses, including soy oil, soy sauce, soy milk, dofu and TVP (textured
vegetable protein made from soy flour).
(a) Soy sauce is produced by the fermentation of soy beans by the mould Aspergillus oryzae. The
distinctive salty taste of the sauce is due to salts of glutamic acid formed during fermentation.

glutamic acid
(i)

Explain what is meant by the term pKa as applied to a weak acid HA.

There are three pKa values associated with glutamic acid: 2.1 , 4.1 and 9.5.
(ii)

Make use of these pKa values to suggest the major species present in solutions of
glutamic acid with the following pH values.

pH 1

pH 3

pH 7

pH 11

[6]
(b) Dofu is made by coagulating soy milk and then pressing the curds between fine cloth to
extrude most of the moisture. Coagulating agents that have been used include certain salts,
acids or enzymes. Coagulation is due to the denaturation of the proteins in the soy milk.
[You may find that including suitable sketches or diagrams will help you in your answers to
parts (i), (ii) and (iii).]
(i)

What aspect of a protein's structure is altered during coagulation , and why does this
occur?

The calcium salts CaS04 and CaCl 2 are often used to produce dofu.
(ii)

Suggest how Ca 2+(aq) ions can interact with a protein to bring about denaturation.

(iii)

Suggest how a weak acid might interact with a protein to bring about denaturation.

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The addition of glucono-delta-Iactone, GDL, to soy milk produces a soft form of dofu due to a
gradual acidification of the mixture. In aqueous solution the following equilibrium is slowly set
up.

OH

HO
HO

HO

H2O

OH

HO

OH

C02H

OH
OH

GDL

gluconic acid

When 1.00g of GDL (Mr = 178) was dissolved in 50.0cm 3 water and the solution allowed to
reach equilibrium, the concentration of gluconic acid was found to be 0.0670 mol dm-3 .

(iv)

Write an expression for Kc for the equilibrium above, and use the data given to calculate
its value. You can assume that [H 20] = 55.5 mol dm-3 throughout.

[8]

(c) Soy beans, and especially the dofu made from them, are a good source of dietary isoflavenoids,
which are claimed to help in the prevention of some cancers. The major isoflavenoid in soy is
diadzein.
HO

OH

diadzein
(i)

Draw the structural formula of the compound formed when diadzein reacts with an excess
of Br2 (aq).

When diadzein is treated with H2 and Ni, compound F, C1sH1404' is formed. One mole of
compound F reacts with three moles of sodium metal. F also dissolves in NaOH(aq). F reacts
with acidified K2Cr20 7 to give compound G, C1sH1204' which gives an orange precipitate with
2,4-dinitrophenylhydrazine reagent.

(ii)

Suggest a structural formula for F and for G, identifying any chiral carbon atoms. Explain
the reactions which occur.
[6]
[Total: 20]

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6
3

The direct oxidation of alcohols in a fuel cell represents potentially the most efficient method of
obtaining useful energy from a renewable fuel.
(a) The first alcohol to be used successfully in a fuel cell was methanol. At the anode methanol
and water undergo the following reaction.

The electrons pass around the external circuit to the cathode.

The protons move through the conducting polymer electrolyte to the cathode, where they
react with oxygen, producing water.
(i)

Construct an equation for the cathode reaction .

(ii)

Hence construct the equation for the overall reaction , showing your working.

(iii)

The cell is capable of producing an e.m.f. of 1.18V. By using suitable data from the Data
Booklet, suggest a value for the E-& of the CO:!CH 3 0H electrode reaction .

(iv)

Suggest a possible advantage of using the methanol fuel cell compared to a hydrogen
(H:!02) fuel cell.
[5]

(b) Ethanol is also being investigated as a possible fuel in fuel cells.

(i)

Write the equation for the complete combustion of 1 mol of ethanol.

(ii)

The standard enthalpy change of combustion of ethanol , t1H ~ has a value of

-1367kJ mol- 1, and the entropy change for the same process is -140J mol- 1 K - 1.
Calculate the standard Gibbs free energy change, t1GB; for the combustion of ethanol at
298K.

(iii)

t1G-&and Etell are related by the following equation.

E-& - -t1G-&
cell-

zF

where t1G-& is the standard free energy change in joules per mole, z is the number of
moles of electrons transferred during the redox reaction and F is the Faraday constant.
Use the equation you have written in (i) to decide on a suitable value for z, and hence
calculate the Etell for the ethanol/oxygen fuel cell.
[4]

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(c) (i)

Use suitable bond energy values from the Data Booklet to calculate llH for the combustion
of one mole of ethanol according to the equation you have written in (b)(i) . Use a value of
805 kJ mol-1 for the bond energy of each C=O bond in CO 2 .

(ii)

Suggest a reason for the difference between your calculated value and that given in
(b)(ii).
[3]

(d) Alcohol J, CJiyOH, is a volatile fungal metabolite whose presence when detected in air can
indicate hidden fungal attack on the timbers of a house.
When 0.1 Ocm 3 of liquid J was dissolved in an inert solvent and an excess of sodium metal
added, 10.9 cm 3 of gas (measured at 298 K) was produced.
When 0.1 Ocm 3 of liquid J was combusted in an excess of oxygen in an enclosed vessel, the
volume of gas (measured at 298 K) was reduced by 54.4 cm 3 . The addition of an excess of
NaOH(aq) caused a further reduction in gas volume of 109 cm 3 (measured at 298 K).

(i)

Use these data to calculate values for x and y in the molecular formula CJiyOH for J.

Alcohol J reacts with acidified K2 Cr2 0 7 , and can be dehydrated to alkene K. On treating K
with an excess of hot acidified concentrated KMn0 4 , an equimolar mixture of ethanoic acid
and propanone is produced.
(ii)

Use this information to deduce the structural formulae for J and K, explaining your
reasoning.

(iii)

Suggest suitable reagents and conditions for the conversion of J into K.

(iv)

Explain whether K can show geometrical isomerism.

[8]
[Total: 20]

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(a) Describe what is meant by the term nucleon number.

[1 ]

(b) State two ways in which the behaviour of electrons in an electric field differs from that of
protons.
[1]
(c)

(i)

Draw dot-and-cross diagrams to show the bonding in the molecules of N0 2 and 0 3'
Each molecule contains a dative covalent bond.
In the N02 molecule the central atom is nitrogen.
In each case you should distinguish carefully between electrons originating from the
central atom and those from the two outermost atoms.
Include all lone pairs in your diagrams.

(ii)
(iii)

Suggest a value for the bond angle in each of the above two molecules, giving reasons
for your choice.
The compound F02 does not exist, but C10 2 does.
By considering the possible types of bonding in the two compounds, suggest reasons
for this difference. (Assume that the halogen atom occupies a central position in each of
these molecules.)
[6]

(d) (i)

Describe how you could carry out the reaction between calcium and oxygen, and state
what you would observe during this reaction .

(ii)

The pH values of the solutions formed when the oxides of Group 11 are separately shaken
with water increase from magnesium to barium.
Explain why this is the case.
[3]

(e) When ozone, 0 3' is passed over dry powdered BaO at -10 C, barium ozonide, Ba(03)2' is
formed as a red-brown solid.
Adding water to the solid and warming to room temperature causes a reaction to occur.
Oxygen gas is produced and an alkaline solution is left.
Suggest a balanced equation for the reaction between barium ozonide and water.
[1]

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(1)

Ozone is usually made by passing oxygen gas through a tube between two highly charged
electrical plates.

The reaction does not go to completion , so a mixture of the two gases results.
The concentration of 0 3 in the mixture can be determined by its reaction with aqueous Kl.

The iodine formed can be estimated by its reaction with sodium thiosulfate.

When 500cm 3 of an oxygen/ozone gaseous mixture at s.t.p. was passed into an excess of
aqueous KI , and the iodine titrated , 15.0cm 3 of 0.100moldm- 3 Na 2S20 3 was required to
discharge the iodine colour.

(i)

Calculate the amount in moles of iodine produced.

(ii)

Hence calculate the percentage of 0 3 in the gaseous mixture.

[3]

(9) Oxidation is an important reaction in organic chemistry. Both aldehydes and carboxylic acids
can be prepared by the oxidation of alcohols with acidified K2Cr207.
(i)

Describe how you could ensure that only either the aldehyde or the carboxylic acid is
produced during the oxidation process.

(ii)

Compounds L and M, both Cg H 10 , and compound N, Cg H120 , are all oxidised by hot
concentrated alkaline KMn04 ' followed by acidification, to give benzene-1 ,2-dicarboxylic
acid, P.

P
Compound L reacts with Br2(aq), but compound M does not.
Compound N reacts with alkaline aqueous iodine.
Suggest structures for compounds L , M and N.
[5]
[Total: 20]

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10
5

(a) Copper minerals often contain copper sulfide mixed with the sulfides of silver and zinc. After
roasting in air to produce the oxides and reduction to the crude metals with carbon, the solid
impure copper is purified by electrolysis.
Describe the electrode reactions that take place during this electrolysis, and explain in detail
how each of the two impurity metals is removed from the copper.
[4]

(b) Describe the colour changes observed when dilute aqueous ammonia is added to a solution
containing Cu 2 +(aq) until the ammonia is in an excess, giving the formulae of all relevant
copper compounds.
~]
(c) When black copper(II) oxide is stirred with liquid ammonia, it dissolves to give a coloured
solution. During this reaction the oxide ion is acting as a Bmnsted-Lowry base.
Suggest an equation for this reaction, and suggest the colour of the solution.
[2]

(d) When concentrated hydrochloric acid is added to a solution containing Cu 2+(aq) , the colour
changes to a pale yellow-green. No gas is evolved.
No such colour change occurs when concentrated sulfuric acid is added to Cu 2+(aq).
Dilution of the yellow-green solution with water produces the original pale blue colour.
Suggest an explanation of these observations.
[3]
(e) Adding KI(aq) to a solution containing Cu 2+(aq) causes a reaction to take place, which
produces purple-brown iodine and a white precipitate of the highly insoluble copper(I) iodide,
CuI.
(i)

Construct a balanced equation for this reaction.

(ii)

By selecting appropriate EB- values from the Data Booklet, explain why it would be
expected that this redox reaction would not occur.

(iii)

Suggest a possible reason for why it does in fact occur.

[4]

(f)

An alkaline solution of complexed Cu 2+(aq) is used in organic chemistry to test for a particular
functional group.

(i)

Describe the appearance of a positive result of this test.

(ii)

Draw the displayed formulae of two compounds with the molecular formula CSH100 that
would show a positive result in this test, and the displayed formula of one compound with
the same molecular formula that would not. Label your structures clearly.
[3]
[Total: 20]

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reasonable effort has been made by the publisher (UCLES) to trace copyright holders, but if any Items requiring clearance have unwittingly been included, the
publisher will be pleased to make amends at the earliest possible opportunity.
University of Cambridge International Examinations is part of the Cambridge Assessment Group. Cambridge Assessment is the brand name of University of
Cambridge Local Examinations Syndicate (UCLES) , which is itself a department of the University of Cambridge.

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