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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

CANDIDATE

NAME

CENTRE
NUMBER

ITllJ

INDEX
NUMBER

9647/02

CHEMISTRY
Paper 2 Structured Questions

October/November 2011
2 hours

Candidates answer on the Question Paper.

Additional Materials:

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.
DO NOT WRITE IN ANY BARCODES.
Answer all questions.
A Data Booklet is provided.
At the end of the examination, fasten all your work securely together.
The number of marks is given In brackets [ 1at the end of each question or part
question.

For Examiner's Use

-_

1
..._---

2
3

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5
- -----6

--

Total

....

~- - - _ . -

This document consists of 13 printed pages and 3 blank pages.

~Sln.o,Drn E"'m'oatl'"s on. ,......ment B",

e UCLES & MOE 2011

DC (LEO) 25669f7

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UNIVERSITY of CAMBRIDGE

International Examinations
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1
Planning (P)

For

Ex8JrJner's

Aspirin was one of the first drugs to be produced synthetically and is one of the most widely
used 'over-the-counter' drugs in the world. It is a white solid and is prepared by an acylation
reaction between 2-hydroxybenzenecarboxylic acid and ethanoic anhydride.
The other product of this reaction is ethanoic acid.

2-hydroxybenzenecarboxylic acid

ethanoic anhydride

aspirin

2-Hydroxybenzenecarboxylic acid is a white crystalline solid.

Ethanoic anhydride is a corrosive llquid which has a density of 1.08gcm-3.
Pure aspirin has a melting point of 135C.
Like most organic reactions, the yield of this react ion is less than 100%. Using the procedure
described below, a typical yield of pure aspirin is 75 %.
Equimolar amounts of 2-hydroxybenzenecarboxylic acid and ethanoic anhydride are used,
together with about 8-10 drops of 85 % phosphoric acid which catalyses the reaction. When
mixing the reactants, the initial reaction may be violent.
The reaction mixture is then heated under reflux conditions for around fifteen minutes.
About 2-3cm 3 of water is then added to the hot reaction mixture to hydrolyse any unreacted
ethanoic anhydride. The addition of this water may cause the mixture to boil.
Once the reaction has subsided, the reaction mixture is poured into about 50cm 3 of
cold water. This causes the aspirin to precipitate. The crude aspirin product is purified by
recrystallisation from water.
(a) Using the information given above:
(I)

(ii)

write a balanced equation for the formation of aspirin;

calculate the masses of reactants you would use to prepare 10g of pure aspirin,
showing your working.

[3)

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(b) Write a plan for the preparation of 1Og of pure aspirin.

For
EtHmlner's

In your plan you should:

Use

draw a diagram of the assembled apparatus you would usa when heating the
reaction mixture;
give a full description of the procedures you would use to prepare and purify the
aspirin ;
explain how you would check the purity of your sample .

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For
.... .. .. ... ... . ...... . .. .. .. ... .... .. .. .

Examiner's

Use

I!

11 1

........... ........... ...................... ................. ......................................... .............................. .. [8]

(c) Identity one potential safety hazard in this experiment and state how you would
minimise this risk .

...... ... ........................... ...... ................. ..... .... ... .... ......... .................. ..... ....... ... .... ..... ... ... .. [1)

[Total: 12]

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Phosphorus(V) chloride, PCls' is a white solid which sublimes at 160 "C.

For
Examiners

When gaseous phosphorus(V) chloride is heated in a closed container, the following

equilibrium is established.

USB

(a) Write an expression for Kc for this equilibrium, stating the units .

[2]
Phosphorus(V) chloride dissolves in some polar solvents without reaction and such solutions
conduct electricity. This is due to the presence of the two ions [PClJ+ and [PCIJ- ,
(b)

Draw the structure and suggest the shape of each of these ions.

[3]
(Total: 5]

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This question refers to the equilibrium in question 2.

For
EJlflmin9f's

Usa

In an experiment, 1.00mol of PC's vapour was heated in a closed S.OOdm 3 flask at SOOK
until equilibrium had been established.
The gases in the flask were then rapidly cooled, causing the formation of crystals of pels
and liquid PCl3. The chlorine gas present was pumped away and collected.
The amount of chlorine collected was x mol.
An excess of water was then very carefully added to the two remaining compounds, under
suitable conditions, causing the following reactions to occur.

PCIS + 4H20 -) 5HCl + H3 P0 4

PCl3 + 3H 20

3HCl + H3P03

You may assume that both H3 P0 4 and H3 P0 3 behave as dibasic (diprotic) strong acids.

(a) Determine, in terms of X, the number of moles of H+that will be formed after the addition
of water to the mixture of PCls and PCI3 "

[4)

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The resulting solution was made up to 1.00 dm 3 in a standard flask. 25.0cm 3 of this solution
was titrated with 4.00 mol dm-3 NaOH and required 37.4 cm 3 for neutralisation.

(b) (i)

Calculate the total amount, in moles, of H+ ions present in the 1.00dm3 standard
flask.

(II)

Use your answers to 3(a) and 3(b)(i) to calculate the amounts, in moles, of PCI 5 ,
PCla and Cl 2 in the original equilibrium at 500 K.

Foi
Examiner's
Use

[4J
(e) Use your answers to question 2(a) and 3(b)(ii} to calculate a value for Kc for the
equilibrium.

[2]
[Total: 1Dj

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The elements of Group It, magnesium to barium, are metals while the elements of Group VII,
chlorine to iodine, are non -metals.

(a)

(I)

State one physical property of the elements of Group II which shows them all to be
metals.

(ii)

State one trend in the physical properties of the elements of Group VII from chlorine
to iodine, and explain Why this change occurs.
change

explanation

For
Examiner's
Use

.................. ...................... ........................ ........................ ...................... ... ............. [4]

Among the elements of Group IV, those towards the top, carbon to germanium, have very
different properties from those at the bottom, tin and lead.
For example, the melting points show a marked change after germanium .
element

Si

Ge

Sn

Pb

mp/oC

>3550

1410

937

232

327

(b) Carbon, silicon and germanium each form a solid with the same type of structure.
(I)

(ii)

What type of structure is present in solid carbon, silicon and germanium?

Suggest why the melting points 01 these elements decrease from carbon to
germanium .

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

Carbon and silicon each form a tetrachloride. CCl4 has no reaction with water; SiCl4 reacts
violently with water.

(e)

(I)

Write a balanced equation for the reaction of SiCl4 with water.

~ ~ r

(il)

i .

.. A'

Use the Data Booklet to obtain values for the C-Cl and Si-Cl bond energies.
C-Cl

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(III) Suggest an explanation for the inertness of CC14 to water.

For
ExaminBJ's

Use

..............................................................................................................................[3]
Lead forms two chlorides, PbCl2 and PbCl4 .
When chlorine is passed into a saturated solution of PbCl2 in NH4Cl(aq), a yellow salt, V, is
formed which has the following composition by mass:

ci, 46.7%; H, 1.76%; N, 6.14%; Pb 45.4%.

V is ionic with a formula mass of 456. One formula unit of Y contains one type of anion and
one type of cation in the ratio 1:2.
(d) (l)

(II)

Calculate the empirical formula of Y.

Suggest the formulae of each of the ions present in V.

anion

cation

(iii)

What is the oxidation state of Pb in Y?

(Iv)

Suggest the shape of the lead-containing ion.

(5]

When Y is treated with cold concentrated H2S04 , PbCl4 is formed as an oily liquid.
(e)

By using appropriate values from the Data Booklet, predict what, if anything, will happen
when a solution of PbCl4 in hydrochloric acid is added to a solution containing V3+(aq).

[2]
[Total: 17]

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Compound K has the molecular formula C 4H a0 2

for
ExBlTliner's

USe

K decolourises aqueous bromine.

When O.10mol of K is reacted with an excess of sodium metal, 2.4dm 3 of hydrogen are
formed, measured at room temperature and pressure.

(a) Use all of the above information to determine the identity and number of each of the
functional groups present in compound K.
For each functional group you identify, explain how you came to your decision .
(I)

(II)

reaction with aqueous bromine

reaction with sodium metal

(5]

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(b) Draw the displayed formulae of all the possible stereoisomers of K which have the
following features.

For
Examiner's

US8

They have molecular formula C4H a0 2 and give the reactions on page 10.

No oxygen atom is attached to any carbon atom which is involved in a double bond.

No carbon atom has more than one oxygen atom joined to it.

For each structure you draw, state the type of stereoisomerism it shows and give one
further piece of relevant information about it.
You are not required to label functional groups.

[7]
[Total: 12]

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6 Compound W has the molecular formula C7H 70Cl. It is an aromatic compound which
contains two functional groups.
Data about the reactions of Ware given in the table.

._- ,-_.....

reaction

reagent

AgN03(aq). warm

Br2(aq)
in an excess

Mn04-/OHheat under reflux

then acidify
Na

.._...

Fol
ElI8mlner's

Use

.....

result

I white solid formed which is soluble in an

i, excess of NH3(aq)
I, white solid formed which has Mr =379.2
I

I
I

----_._-

I Mn0 4 - is decolourised;

one organic product formed with Mr

= 138

._._.!,

colourless gas evolved;

white solid formed which is soluble in H2O

NaOH(aq) at room
I temperature

-- _.-

'--

1---'--'-

..

colourless solution formed

- -..-._-.

In this question, when identifying functional groups, your answers should be unambiguous.
(8)

(I)

What is the white solid that is formed in reaction 1?

(II)

Name the functional group that reaction 1 shows to be present in W.

(iii)

Based only on reaction 4, give the names of two different functional groups that
could be present in W .
.................................. and

(iv)

Which of the functional groups you have named in (III) is confirmed by reaction 5?
Explain your answer.

.............................................................................................................................. [5]
(b) Deduce the molecular formula of the organic product formed in reaction 3.

[1]

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(e)

(i)

Deduce the molecular formula of the white solid formed in reaction 2.

For
Examiner's

U$(J

(II)

What type of reaction takes place in reaction 2?

(ill)

Explain clearly how the formation of this compound shows that compound W is an
aromatic compound rather than an aliphatic compound.

(Iv)

Name the functional group present in W that is confirmed by reaction 2.

(v)

Which other reaction confirms that W is aromatic? Explain your answer.

reaction

.............................................................................................................................. [6]
(d) You now have enough information to determine the structural formula of W.
(i)

(Ii)

Draw the fully displayed structure of W.

Explain clearly why you have placed each of the two functional groups in their
particular positions .

.............................................................................................................................. [4]
[Total: 16]

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Permission to reproduce ~ems Where third-party owned matorial protected by copyright is included has been sought and cleared where possible. Every
reasonable effort has been made 'at the publisher (UClES) to trace copyright holders, but II any hems requiring clearance have unwIttingly been included, the
publisher wW be pleased 10make amends at the earliest possible opportun~.
Univol5ity of Carrt>rll1ge International Examlnatlons is part of the Cambridge Assessment Group. Cambridge Assessmem ts the brand name of University 01
Cambridge Local ExaminaUons Syndicate (UCLES), which Is itseW a department of Ihe University of Cambridge .

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