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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 9746/01
READ THESE INSTRUCTIONS FIRST
Write in soft pencil.
Do not use staples, paper clips, highlighters, glue or correction fluid.
Write your name, Centre number and index number on the Answer Sheet in the spaces provided unless
this has been done for you.
Paper 1 Multiple Choice
Additional Materials: Multiple Choice Answer Sheet
Data Booklet
October/November 2007
1 hour
There are forty questions on this paper. Answer all questions. For each question there are four possible
answers A, B, C and D.
Choose the one you consider correct and record your choice in soft pencil on the separate Answer Sheet.
Read the instructions on the Answer Sheet very carefully.
Each correct answer will score one mark. A mark will not be deducted for a wrong answer.
Any rough working should be done in this booklet.
This document consists of 14 printed pages and 2 blank pages.

'SIIIIB,..--"
Examinations and Assessment Board

UNIVERSITYof CAMBRIDGE
International Examinations
UCLES & MOE 2007 [Turn over
2
Section A
For each question there are four possible answers, A, B, C, and D. Choose the one you consider to
be correct.
1 Naturally occurring silicon is a mixture of three isotopes, ?8Si, 29Si and 30Si. The relative atomic
mass of silicon is 28.109.
What could be the relative abundance of each of the three isotopes?
A 91.1 % 28Si, 7.9 %29Si and 1.0 0A, 30Si
B 92.2 % 28Si, 4.70/0 29Si and 3.1 % 30Si
C 95.0 % 28Si, 3.2 % 29Si and 1.8 0A, 30Si
D 96.3 % 28Si, 0.3 %29Si and 3.4A, 30Si
2 When iron is reacted with aqueous iron(III) ions, iron(II) ions are formed.
Assuming the reaction goes to completion, how many moles of Fe and of Fe
3
+(aq) would result in
a mixture containing equal numbers of moles of Fe
3
+(aq) and Fe
2
+(aq) once the reaction had
taken place?
moles of Fe moles of Fe
3
+(aq)
A 1 2
B 1 3
C 1 5
D 2 3
3 An excess of cold water was added to 0.3 mol of a chloride of the third period of the Periodic
Table at room temperature.
0.6 mol of HCI was formed.
Which chloride was treated?
A MgCl
2
B AICl
3
C PCls D SiC4
4 Use of the Data Booklet is relevant to this question.
What do the ions
36
8
2
- and 37CI- have in common?
A Both ions have more electrons than neutrons.
B Both ions contain the same number of nucleons in their nuclei.
C Both ions have an outer electronic configuration 2s
2
2p6.
D Both ions have 20 neutrons in their nuclei.
UCLES &MOE 2007 9746/01/0/N/07
3
5 The table gives the successive ionisation energies for an element X.
1st 2nd 3rd 4th 5th 6th
ionisation energyI kJ mor
1
950 1800 2700 4800 6000 12300
What could be the formula of the chloride of X?
A XCI o XC4
6 Which molecule has the largest dipole?
A B c
CI
/
O=C
"-
CI
o
7 The diagram below shows the structure of part of a crystal of ice.
.... I' #
.... H ,I' H"
,,:/
o
H
. I
'. 0
H/ \.
Which statement is correct?
A All the bond angles surrounding each oxygen atom are 120
0

B Four electrons from each oxygen are involved in forming hydrogen bonds.
C The hydrogen bonds, shown by the dotted lines, are stronger than the O-H covalent bonds.
o The open structure of ice causes ice to be denser than water.
UCLES & MOE 2007
9746/01/0/N/07
[Turn over
4
8 A molten chloride of a Group I metal, XCl, and a molten chloride of a Group II metal, YCl2 , are
separately electrolysed using the same current for the same time.
Which statement about this experiment is correct?
A An equal number of moles of X and Y is deposited.
B Equal masses of X and Yare deposited.
C The number of moles of Y deposited is half the number of moles of X deposited.
D YCl
2
gives off twice the volume of chlorine gas as XCl, measured under the same conditions
of temperature and pressure.
9 A 25 cm
3
sample of 0.20 mol dm-
3
Tl + NO; required 25 cm
3
of 0.10 mol dm-
3
acidified KMn04 to
oxidise it to Tl
3
+ in solution.
What is the oxidation state of the manganese in the reduced form?
A 2 B 3 C 4 D 7
10 Some relevant redox half-equations are given in the table.
half-equation E?/V
1
2
(aq) + 2e- ~ 2I-(aq) +0.54
2H+(aq) + 02(g) + 2e- ~ H
2
0
2
(aq) +0.68
H
2
0
2
(aq) + 2H+(aq) + 2e- ~ 2H
2
O(I) +1.77
What will be observed when a few drops of acidified aqueous hydrogen peroxide are added to an
excess of aqueous potassium iodide?
A The solution turns brown and effervescence occurs.
B The solution turns brown without effervescence.
C The solution turns purple and effervescence occurs.
D The solution turns purple without effervescence.
UCLES & MOE 2007 9746/01/0/N/07
5
11 Values for the ionic product of water, K
w
, at two different temperatures are given below.
temperature/DC K
w
/moI
2
dm-6
25 1.00 x 10-
14
30 1.44 x 10-
14
What is correct for pure water at 30C?
A [H+] > [OH-]
B [H+] =1.44 x 10-
7
mol dm-
3
C pH<7
o pH= 7
12 The pH change when 0.100 mol dm-
3
NaOH is added dropwise to 10.0 cm
3
of a 0.100 mol dm-3
solution of a weak acid is shown below.
Where on the graph does pH = pK
a
where K
a
is the acid dissociation constant of the weak acid?
14
12
10
8
B
pH
6 A
4
2
0
0 2 4 6
o
C
8 10 12 14 16 18
volume ofO.100moldm-
3
NaOH added/cm
3
13 The pH of human blood is constant at about 7.40.
Which ion or molecule present in the human body will remove contaminating H+(aq) ions from the
blood to keep the pH constant?
A C0
2
-
3
B HCO; C o
P03-
4
UCLES & MOE 2007 9746/01/0/N/07 [Turn over
6
14 The reaction of manganate(VII) ions with ethanedioate ions in acid solution may be represented
by the following equation.
The graph shows concentration of manganate(VII) ions against time for this reaction.
What does the shape of the graph suggest about this reaction?
A It is exothermic.
B It is endothermic.
C It shows first order kinetics.
D It produces its own catalyst.
15 What is not a trend from left to right across the elements of the third period of the Periodic Table?
A The radii of the atoms decrease.
B The oxides of the elements change from basic to acidic.
C The melting points of the elements decrease steadily.
D The compounds of the elements change from ionic to covalent.
16 The ash from burnt seaweed contains chlorides and iodides of some Group I and Group II
elements. Some seaweed ash was treated with concentrated sulphuric acid and the resulting
fumes passed first through a cold tube and then bubbled through aqueous silver nitrate.
What would be observed during the experiment?
inside the cold tube with aqueous silver nitrate
A black deposit white precipitate
B black deposit yellow precipitate
C no deposit white precipitate
D no deposit yellow precipitate
UCLES & MOE 2007 9746/01/0/N/07
7
17 What is observed when magnesium chloride is added to water?
solubility in water pH of resulting solution
A dissolves 2
B dissolves 6.5
C insoluble 7
D very slightly soluble 8
18 Use of the Data Booklet is relevant to this question.
Which particle contains a single unpaired electron?
A a molecule of H
2
S
B one of the particles formed after the heterolytic fission of a chlorine molecule
C the ammonium ion in NH
4
CI
D the copper ion in CuO
19 A compound X is optically active. One mole of X liberates one mole of hydrogen when it reacts
with sodium.
What could be the formula of X?
A CH
3
CH(OH)CHO
B CH
3
CH(OH)C0
2
H
C HOCH
2
CH(CH
3
)CH
2
OH
D HOCH
2
CH
2
C0
2
H
20 Bupropion is an anti-depressant used in the treatment of hyperactive children and adults.
CH
3
CH3fNHCH(CH3)CO-<Q
CH3 CI
bupropion
Which deduction about bupropion can be made from this structure?
A It contains an amide linkage.
B It gives a phenol on heating with aqueous sodium hydroxide.
C It is optically active.
D Its aqueous solution is acidic.
UCLES & MOE 2007 9746/01/0/N/07 [Turn over
8
21 Aldehydes and ketones are produced industrially by the catalytic oxidation of alkenes. For
example, ethanal is manufactured from ethene as shown.
The process is also used industrially with but-2-ene, CH
3
CH=CHCH
3
.
Which compound is obtained from but-2-ene?
A CH
3
CH
2
CHO
B CH
3
COCH
2
CH
3
C CH
3
CH
2
CH
2
CHO
D (CH3)2CHCHO
22 Hydrogen iodide undergoes an addition reaction with propene forming 2-iodopropane. When
propene is bubbled through iodine monochloride, ICI, dissolved in a suitable solvent, a similar
reaction occurs.
Which product will be present in the greatest yield?
A CH
3
CHCH
2
CI
I
CI
B CH
3
CHCH
2
1
I
I
C CH
3
CHCH
2
1
I
CI
D CH
3
CHCH
2
CI
I
I
23 Chlorofluorocarbons (CFCs) have been widely used in aerosol sprays, refrigerators and in
making foamed plastics, but are now known to destroy ozone in the upper atmosphere.
What will not destroy ozone, and therefore can be used safely as a replacement for CFCs?
A CHBr3
B CCl3CBr3
C CHCIFCCIF
2
D CH
3
CH
2
CH
2
CH
3
UCLES & MOE 2007 9746/01/0/N/07
9
24 A solid compound Z dissolved readily in water to give a weakly alkaline solution. On evaporation
of the water, Z was recovered unchanged.
What could Z be?
A CH NWCZ-
3 3
B CCl
3
C0
2
Na+
C
C
6
H
s
O-Na+
D H
2
NCH
2
C0
2
H
25 Which compound reacts with ammonia?
A bromoethane
B chlorobenzene
C ethanol
D phenol
26 All the isomeric alcohols with the molecular formula C
S
H
12
0 are added separately to warm
alkaline aqueous iodine.
How many of the isomers will give a yellow precipitate? (Ignore stereoisomers.)
A 0 B 1 C 2 D 3
27 Which reaction yields a carbon compound incorporating deuterium, O? [0 =2H]
NaOO
A CH
3
CH
2
CN

O
2

B CH
3
CD(OD)C0
2
H
acidified KMn0
4

heat
NaOO
UCLES &MOE 2007
heat
9746/01/0/N/07 [Turn over
10
28 N-Methyl-D-aspartic acid is a neuroprotective agent which is used in the treatment of strokes,
trauma and epilepsy. Its structure is shown.
Which statement is not correct?
A It is optically active.
B It reacts with ethanol to form an ester.
C It reacts with ethanoyl chloride to form an ester.
D It reacts with phosphorus pentachloride to form an acyl chloride.
29 Which salt will be the most acidic in aqueous solution?
B C
6
H
s
NH; CZ-
C K+CZ-
D NH; CZ-
30 Which structure will be present when the amino acid aspartic acid,
is in aqueous solution at pH10?
A B C D
+ + +
H
3
NCHC0
2
H H
3
NCHC0
2
H
3
NCHC0
2
H H
2
NCHCO;
I I I I
CH
2
CH
2
CH
2
CH
2
I I I I
C0
2
H C0
2
H CO; CO;
UCLES &MOE 2007 9746/01/0/N/07
11
Section B
For each of the questions in this section, one or more of the three numbered statements 1 to 3 may
be correct.
Decide whether each of the statements is or is not correct (you may find it helpful to put a tick against
the statements that you consider to be correct).
The responses A to D should be selected on the basis of
A B C D
1,2 and 3 1 and 2 2 and 3 1 only
are only are only are is
correct correct correct correct
No other combination of statements is used as a correct response.
31 Which systems contain delocalized electrons?
1 cyclohexene
2 graphite
3 sodium
32 Calcium reacts with water to form calcium hydroxide and hydrogen.
The standard enthalpy change for this reaction can be measured in the laboratory.
What further information is needed in order to calculate the standard enthalpy change of
formation of calcium hydroxide, tiH1?
1 tiH1 for H
2
0(I)
2 tiH1 for H
2
(g)
3 first and second ionisation energies of Ca
33 A theoretical reaction involves P + Q ~ product.
The rate equation is rate =k[P][QYand the units of the rate constant, k, are molY dm
z
s-
1

Which sets of values of x, y and z fit the above information?


x y z
1 0 -1 +3
2 1 -1 +3
3 2 -2 +6
UCLES & MOE 2007 9746/01/0/N/07 [Turn over
12
The responses A to D should be selected on the basis of
A B C D
1,2 and 3 1 and 2 2 and 3 1 only
are only are only are is
correct correct correct correct
No other combination of statements is used as a correct response.
34 Which statements about the elements calcium, strontium and barium are correct?
1 The ionic radius of the M
2
+ ion increases from calcium to barium.
2 The magnitude of the hydration energy of the AK-+ ion increases from calcium to barium.
3 The energy required for the process M(g) ~ AK-+(g) + 2e- increases from calcium to barium.
35 Use of the Data Booklet is relevant to this question.
By using the relevant I? values, which halogens will oxidise Fe
2
+(aq) to Fe
3
+(aq)?
1 chlorine
2 bromine
3 iodine
36 Use of the Data Booklet is relevant to this question.
Which of the following are chemically stable when left to stand in the atmosphere?
1 A solution of potassium hexacyanoferrate(III).
2 A solution of chromium(II) chloride.
3 A mixture of aqueous sodium hydroxide and iron(II) sulphate.
UCLES & MOE 2007 9746/01/0/N/07
13
37 Capsaicin is the substance in chilli peppers which causes the hot sensation when it is eaten.
The CH
3
0- group is inert.
Which reactions will capsaicin undergo?
1 Addition of bromine in an organic solvent causes three atoms of bromine to be incorporated
into the molecule.
2 On heating with NaOH(aq), two moles of NaOH are used up per mole of capsaicin.
3 On heating under reflux with acidified concentrated KMn04, (CH
3
)2CHCHO is a product.
38 Dinoseb is a herbicide.
N0
2
dinoseb
Which statements about dinoseb are correct?
1 Its aqueous solution is acidic.
2 It can exist in optically active forms.
3 It reacts with ethanol in the presence of concentrated sulphuric acid to give an ester.
39 Nail varnish consists of a mixture of pigments, gloss, plasticizer and adhesive dissolved in a
suitable solvent. A common solvent is a mixture of propanone and pentyl ethanoate,
CH3C02(CH2)4CH3.
Which reagents will give a yellow or orange precipitate with this solvent?
1 2,4-dinitrophenylhydrazine reagent
2 alkaline aqueous iodine
3 Fehling's reagent
UCLES & MOE 2007 9746/01/0/N/07 [Turn over
14
The responses A to 0 should be selected on the basis of
A B C 0
1,2 and 3 1 and 2 2 and 3 1 only
are only are only are is
correct correct correct correct
No other combination of statements is used as a correct response.
40 The diagram shows the structure of salicylic acid.
salicylic acid
Which compounds give salicylic acid on acid hydrolysis?
1
CaCl
(rCI
UCLES &MOE 2007
2
6 ~ C O C H 3
9746/01/0/N/07
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
f
) ~
J= CHEMISTRY
,===
~
'= Paper 2 Structured
;===
J===
J iiiiiiiiiiiiii Candidates answer on the Question Paper.
iiiiiiiiiiiiii
~ Additional Materials: Data Booklet
f
READTHESE INSTRUCTIONS FIRST
INDEX
NUMBER
9746/02
October/November 2007
1 hour 30 minutes
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 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 [ ] at the end of each question or part question.
For Examiner's Use
1
2
3
4
5
Total
This document consists of 11 printed pages and 1 blank page.
,+"'''',
-,-"
~ CiVil Singapore Examinations and Assessment Board
. ~
..... ~ ' . . . . UNIVERSITYof CAMBRIDGE
::: International Examinations
@ UCLES &MOE 2007
SP (KN) T32179/5
[Turn over
1
2
When this paper is given in it will go by air to England. Intercontinental jet airliners use
kerosene as fuel. The formula of kerosene may be taken as C
14
H
so
.
(a) To which homologous series does kerosene belong?
...................................................................................................................................... [1]
(b) When kerosene burns in an excess of air, carbon dioxide and water form.
Balance the following equation for the complete combustion of kerosene.
For
Examiner's
Use
............ C
14
H
so
+ 02 ~ CO
2
+ H
2
0 [1 ]
(c) The flight path from Singapore to London is approximately 10700km. A typical
intercontinental jet airliner burns 10.8kg of kerosene for each kilometre covered.
(i) Calculate the mass, in tonnes, of C
14
H
so
burnt on a flight from Singapore to London.
[1 tonne =1 000 kg]
(ii) Use your equation in (b) to calculate the mass of CO
2
produced during this flight.
[3]
UCLES & MOE 2007
9746/02l0/N/07
3
At sea level, an inflated bicycle tyre contains 670cm
3
of air at an internal pressure of
6 bar and a temperature of 20C. The instructions on the side of the tyre state 'Safety note:
maximum internal pressure 8 bar.' At sea level, atmospheric pressure is 101 kPa. The tyre
will burst if the difference between the internal pressure and the external pressure becomes
too great.
[1 bar = 100kPa]
(d) Use the general gas equation PV = nRT to calculate the amount in moles of air in the
tyre at sea level.
[2]
Bicycles may be carried in the luggage hold of an airliner, a part of the aircraft which is not
always heated or maintained at a pressure of 101 kPa. Typical values for the conditions in the
luggage hold of an airliner at a height of 10000 m are a temperature of 5C and a pressure
of 0.28 bar.
(e) A bicycle, with the same tyre inflated at sea level as described above, is placed in the
hold of the airliner.
Assuming the volume of the tyre does not change, calculate the pressure inside the tyre
at a height of 10000 m. Include units in your answer.
[2]
(f) Some airlines insist that bicycle tyres should be deflated before the flight, other airlines
do not.
Should the tyre described above be deflated before flight? Use the data given at the top
of this page and your answer to (e) to justify your reasoning.
...................................................................................................................................... [2]
[Total: 11]
For
Examiner's
Use
UCLES & MOE 2007 9746/02/0/N/07 [Turn over
2
4
Many compounds of chlorine are manufactured from brine, NaCl(aq). The electrolysis of brine
produces C1
2
(g) and NaOH(aq). In some industrial electrolytic cells, these two substances
are allowed to react further. The products formed in this second reaction depend on the
operating conditions used.
(a) Write balanced equations for the reaction between C ~ ( g ) and
(i) cold aqueous NaOH,
(ii) hot aqueous NaOH.
[3]
(b) In each of these reactions, two different chlorine-containing compounds are formed in a
redox reaction.
(i) What is the oxidation number of chlorine in each of the chlorine-containing species
in your equation in (a)(i)? Give your answer in the spaces below.
species
oxidation
species
oxidation
number number
reactant
1><
><
products
(ii) What is unusual about this reaction?
(4]
For
Examiner's
Use
UCLES &MOE 2007 9746/02/0/N/07
5
(c) Chlorine dioxide, Ci0
2
, is used for bleaching paper pulp and for some water treatment.
It is manufactured from CiO; ions in acid solution.
CiO; + 2H+ + e- ~ Ci0
2
+ H
2
0
(i) This reaction may be carried out by using aqueous hydrogen peroxide, H
2
0
2
Use
the Data Booklet to identify the half-equation for H
2
0
2
in this reaction and write it
on the line below.
(ii) Use your answer to (i) to construct the overall equation for the reaction of CiO;
ions with H
2
0
2
in acid solution.
(iii) What is the role of the H
2
0
2
in this reaction?
[3]
[Total: 10]
For
Examiner's
Use
UCLES & MOE 2007
9746/02/0/N/07
[Turn over
6
3 Cobalt forms many complexes with ligands such as H
2
0, NH
s
and CI-.
The most common oxidation states of cobalt are +2 and +3.
Cations containing cobalt in these two oxidation states have significantly different colours
even when the ligands are the same.
Solutions of C0 2+(aq) contain the ion [Co(H
2
0)6]2+.
E6 data for some cobalt complex ions are given below.
[Co(H
2
0)6]S+ + e- ~ [Co(H
2
0)6]2+ E6 = + 1.82V
[Co(NH
s
)6]S+ + e- ~ [Co(NH
3
)6]2+ E6 = + 0.11 V
[Co(H
2
0)6]2+ + 2e- ~ Co + 6H
2
0 E6 =- O.28V
[Co(NH
3
)6]2+ + 2e- ~ Co + 6NH
3
E6 = - 0.43V
CI0
2
acts as a powerful oxidising agent in acid solution.
CI0
2
+ 4H+ + 5e- ~ CI- + 2H
2
0 E6 = + 1.50V
(a) When CI0
2
in acid solution is mixed with Co2+(aq) no significant colour change is
observed.
When Co2+(aq) is mixed with an excess of NH
3
(aq) a slight colour change occurs and
cation P is formed.
When cation P is mixed with CI0
2
in acid solution, a significant colour change occurs.
Use this information and the information given about cobalt above to answer the following
questions.
(i) What is the co-ordination number of Co in [Co(H
2
0)6]2+?
(ii) Why is no significant colour change observed when CI0
2
in acid solution is mixed
with Co
2
+(aq)? Explain your answer.
For
Examiner's
Use
UCLES & MOE 2007 9746/02/0/N/07
7
(iii) Suggest the identity of cation P.
(iv) Suggest what is formed when cation P is mixed with CI0
2
in acid solution and
explain why this reaction takes place.
[6]
[Total: 6]
For
Examiner's
Use
UCLES & MOE 2007
9746/02/0/N/07
[Turn over
4
8
Trichloromethane, formerly known as chloroform, was used as an anaesthetic in
surgery. One reason for it not being used today is that it naturally oxidises to phosgene,
which is highly toxic. .
For
Examiner's
Use
+ 02(g) --7 + 2HCl(g) =-356 kJ mol-
1
(a) Use the value of iiH6 given above and the data below to calculate the standard enthalpy
change of formation of phosgene.
compound iiHf IkJmol-
1
(I) -134
HCl (g) -92
[2]
(b) In order to prevent the oxidation of chloroform, it is kept in dark bottles. What does this
suggest about the nature of this oxidation?
...................................................................................................................................... [1]
(c) In phosgene, the carbon atom is in the centre of the molecule and is attached to both
chlorine atoms and to the oxygen atom.
(i) Draw a 'dot-and-cross' diagram of the phosgene molecule.
(ii) Suggest the size of the Cl-C-Cl bond angle in the COCl
2
molecule.
[3]
(d) Phosgene reacts with NaOH(aq).lt is suggested that the reaction occurs in two stages.
OH- t COCl(OH) Ii CO
2
+ HCl
stage stage
UCLES &MOE 2007 9746/02l0/N/07
9
(i) What type of reaction is occurring in each stage?
stage I .
stage II .
(ii) Suggest a mechanism for stage I. In your answer, show any relevant charges, lone
pairs of electrons and movement of electrons.
[5]
(e) In order to remove any phosgene present in a bottle of chloroform, a small amount of
ethanol is added. Use the information in (d) to suggest the structural formula of the
organic compound formed when phosgene reacts with ethanol.
[1 ]
(f) Phosgene can be converted into urea, CO(NH
2
)2.
(i) Suggest a reagent for this conversion.
(ii) With strong acids urea can act as a base. Suggest why.
[2]
(g) Granular urea can be used to remove N0
2
from the flue gases of power stations where
hydrocarbon fuels are burned in air. Carbon dioxide, water and nitrogen are formed.
(i) Write a balanced equation for this reaction.
(ii) Why is it important to remove N0
2
from the flue gases?
[2]
[Total: 16]
For
Examiner's
Use
UCLES & MOE 2007 9746/02JO/N/07 [Turn over
5
10
The spice cinnamon has been used as a medicine for many hundreds of years.
However, recent research has suggested that cinnamon could also be an effective pesticide
against the larvae of mosquitoes, thus helping in the fight against malaria.
For
Examiner's
Use
Each of the following four compounds, which are present in cinnamon, appears to be effective
as a pesticide.
CH=CHCHO
6CHCH,oCOCH.
OH
CH=CHCH
a
6
OCH
a
CH
2
CH=CH
2
OCH
a
A B C D
The group -OCH
a
which is present in compounds C and D can be regarded as inert.
(a) Only one of the compounds A, B, C or D will react with each of the following reagents.
In each case identify the compound concerned and draw the structural formula of the
organic product formed.
Each compound may be used once, more than once, or not at all.
reagent
compound structural formula
A, B, Cor D of the organic product
CHaCOCl
dilute HN0
3
Na
Tollens' reagent
[8]
UCLES & MOE 2007 9746/02l0/N/07
11
(b) Draw the structural formulae of the organic compounds formed when
(i) compound C is mixed with aqueous bromine;
(ii) compound D is heated under reflux with hot concentrated manganate(VII) ions.
[4]
(c) Compound Amay be converted into compound B in a two-stage process.
(i) What is the structural formula of the intermediate in this conversion?
(ii) For each stage, in the reaction sequence, give reagent(s) and conditions.
stage I
reagent(s) .
conditions .
stage II
reagent(s) .
conditions .
[5]
[Total: 17]
For
Examiner's
Use
UCLES &MOE 2007 9746/02JO/N/07
12
BLANK PAGE
Permission to reproduce items where third-party owned material protected by copyright is included has been sought and cleared where possible. Every
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.
9746/02JO/N/07
MINISTRY OF EDUCATION, SINGAPORE
in collaboration with
UNIVERSITY OF CAMBRIDGE LOCAL EXAMINATIONS SYNDICATE
General Certificate of Education Advanced Level
Higher 2
CHEMISTRY 9746/03
Paper 3 Free Response
Candidates answer on separate paper.
Additional Materials: Answer Paper
Data Booklet
READTHESE 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.
October/November 2007
2 hours
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 11 printed pages and 1 blank page.
~ + o , . ,
- ~
~ 'iiii\ Singapore Examinations and Assessment Board
. ~
UNIVERSITYof CAMBRIDGE
International Examinations
UCLES & MOE 2007 SP (KN) T32390/3 [Turn over
2
Answer any four questions.
1 The "OXO" reaction (reaction I in the scheme below) is industrially important for making alcohols,
aldehydes and carboxylic acids. For example, butan-1-ol, butanal and butanoic acid can all be
synthesised from propene, C
3
H
s
' according to the following scheme.
propene
CH
3
CH
2
CH
2
C0
2
H
Y butanoic acid
CH
a
CH
2
CH
2
CHO(g)
butanal ~
CH
3
CH
2
CH
2
CH
2
0H
butan-1-01
(a) Write an expression for K
p
for reaction I, stating its units. [2]
(b) When an equimolar mixture of CaH
s
' CO and H
2
at an initial total pressure of 120atm is
allowed to reach equilibrium at SOOK, the partial pressure of butanal is found to be 39.6atm.
(i) Calculate the equilibrium partial pressures of C
3
H
s
' CO and H
2

(ii) Hence calculate a value for K


p
at 500 K.
(iii) Suggest, with a reason, whether or not a higher pressure would favour the formation of
butanal.
(iv) Predict the sign of liS for reaction I, showing your reasoning.
(v) The value of ~ G for this reaction is negative. Use this information, together with your
answer to part (iv), to predict the sign of IiHfor reaction I. Explain your reasoning.
(vi) An approximate value for IiH can be calculated using bond energy values. Taking the
bond energy for the C=O bond in carbon monoxide to be 1077kJ mol-
1
, and using
other appropriate bond energies given in the Data Booklet, calculate the value of IiHfor
reaction I.
[7]
UCLES & MOE 2007 9746/03/0/N/07
3
(c) (i) State the reagents and conditions needed for
reaction II,
reaction III.
(ii) State the reagents and conditions needed for the conversion of butan-1-01 into
1-bromobutane,
2-bromobutane (in two steps).
[5]
(d) The compound 2-bromobutane is a useful intermediate for making other organic compounds.
(i) It forms butan-2-ol by heating with NaOH(aq).
How would you expect the rate of this reaction to compare to that of the reaction of
2-iodobutane with NaOH(aq)? Explain your answer.
(ii) Suggest the intermediates and products formed during the following reactions of
2-bromobutane.

reaction with NaCN in alcohol, followed by LiAlH


4
reaction with NaOH in ethanol, followed by cold KMn0
4
(aq)
[4]
(e) When butane is treated with a small quantity of bromine in the presence of ultraviolet light, both
1-bromobutane and 2-bromobutane are produced. Suggest, with a reason, the approximate
ratio in which they are formed. [2]
[Total: 20]
UCLES & MOE 2007 9746/03/0/N/07 [Turn over
4
2 (a) Sketch a graph showing the variation of first ionisation energy across the third period of the
Periodic Table, and explain qualitatively its shape. [3]
The oxides MgO, A ~ 0 3 and Si0
2
are all used as refractory materials due to their high melting points.
The last two are major constituents of gemstones, such as rubies, sapphires and amethysts.
(b) If a sample of one of the oxides was provided as a white powder, describe the reactions you
could carry out on the powder to determine which of the three oxides it was. [3]
(c) When sodium chloride is added to water, a solution is formed which has a pH of 7. When
phosphorus pentachloride is added to water, the resulting solution has a pH of 1. Explain
these observations, and why these two chlorides differ in their reaction with water. [2]
(d) Sulphur dichloride oxide (thionyl chloride), S O C ~ , is a useful reagent in organic chemistry,
converting -OH groups into -Cl groups.
R-OH + S O C ~ --.. R-Cl + HCl + S02
(i) Suggest and explain one precaution you should employ when using S O C ~ in the
laboratory.
(ii) Suggest the equation for the reaction of S O C ~ with water.
(iii) Suggest what you would see when the following are added to separate portions of the
solution resulting from the reaction of S O C ~ with water.
a few drops of AgN0
3
(aq)
a few drops of K
2
Cr
2
0
7
(aq)
Write equations for any reactions that occur.
[6]
UCLES &MOE 2007 9746/03/0/N/07
5
(e) (i) Suggest structures for compounds A and B in the following scheme.
NH
3
O=jNH
A
..
B
..
+
2HCl
C
8
H
6
0
4

0
C
Compound C is a useful intermediate for making primary amines from bromoalkanes, by the
following method.
O=jNH
o
c
II
III
o
(ii) What types of reaction are reactions I, II and III?
(iii) Suggest reagents and conditions for reaction III.
o
OH
OH
[6]
[Total: 20]
UCLES &MOE 2007
9746/03/0/N/07 [Turn over
6
3 (a) Calcium fluoride, CaF
2
, occurs naturally in the mineral fluorspar. It is the major source of
fluorine for the chemical industry, for making PTFE, freons and fire retardants.
(i) Use the following data, together with relevant data from the Data Booklet, to calculate a
value for the lattice energy of CaF
2
(s).
enthalpy change of atomisation of Ca(s) +178kJ mol-
1
electron affinity of fluorine atoms -328kJ mol-
1
enthalpy change of formation of CaF
2
(s) -1220 kJ mol-
1
(ii) Suggest, with reasons, how the magnitude of the lattice energy of CaF
2
(s) might compare
to that of
C a C ~ ( s )
CaO(s).
[5]
(b) Calcium fluoride is sparingly soluble in water. In its saturated solution, the concentration of
CaF
2
is 2.3 x 10-4 moldm-
3

(i) Write an expression for the solubility product, K


sp
' of calcium fluoride, and calculate its
value.
(ii) Use the following data, together with relevant data given in part (a)(i), to calculate a value
for the enthalpy change of solution of calcium fluoride.
ion
~ H e /kJ mol-
1
f
Ca
2
+(aq) -543
F-(aq) -333
(iii) Use your answer to part (ii) to predict whether CaF2 will be more, or less, soluble in hot
water than in cold.
[5]
(c) The melting point of beryllium nitrate, Be(N0
3
)2' is 60 ac, whereas that of calcium nitrate is
561 ac. Magnesium nitrate does not have a recorded melting point because on heating it
decomposes before it melts.
(i) Use these data to suggest the nature of the bonding in beryllium nitrate and in calcium
nitrate, explaining your answer.
(ii) Write an equation for the thermal decomposition of magnesium nitrate, and explain why
calcium nitrate has to be heated to a higher temperature before it decomposes.
[5]
UCLES &MOE 2007 9746/03/0/N/07
7
(d) In 1834 the French chemist Eugene Paligot published his investigations into the action of heat
on the Group II salts of carboxylic acids. He discovered that the salts decomposed to give the
metal carbonate and a carbonyl compound. Thus calcium ethanoate produces propanone.
heat
When this reaction is carried out by heating a 1:1 molar mixture of calcium ethanoate and
calcium methanoate, (HC02)2Ca, a mixture of three carbonyl compounds is formed, all having
M
r
< 60.
(i) Suggest the structures of the three carbonyl compounds, and the ratio in which they
might be produced.
(ii) Suggest two chemical tests that could be used to distinguish the three carbonyl
compounds from each other. You should state what you would observe for each
compound in each test.
[5]
[Total: 20]
UCLES &MOE 2007
9746/03/0/N/07
[Turn over
8
4 (a) (i) Write an expression for the acid dissociation constant, K
a
, for the weak acid hydrocyanic
acid, HCN.
(ii) For HCN, K
a
= 4.9 x 10-
10
mol dm-
3
. Use this value to calculate [H+] in
a 0.100 mol dm-
3
solution of HCN, and hence calculate the percentage of HCN molecules
that are ionised.
(iii) Explain how the addition of solid sodium cyanide, NaCN, will alter the percentage of
HCN molecules ionised.
[5]
(b) (i) What is understood by the term order of reaction?
Cyanohydrins are useful intermediates in organic syntheses. They can be made by reacting
ketones with a solution of HCN to which a small amount of NaCN has been added.
NaCN
(CH3)2CO + HCN - ~ J I (CH
3
)2C(OH)CN
In a series of experiments, the reaction was carried out with different concentrations of the
three reagents, and the following relative initial rates were obtained.
experiment [(CH
3
)2CO] [HCN] [NaCN] relative initial rate
number Imoldm-
3
Imoldm-
3
Imoldm-
3
Imoldm-
3
S-1
1 0.040 0.040 0.008 1.00
2 0.050 0.040 0.008 1.25
3 0.040 0.040 0.006 0.75
4 0.050 0.050 0.006 0.94
(ii) Use these data to deduce the order of reaction with respect to each of the three reagents,
showing how you arrive at your answers. Hence write a rate equation for the reaction.
(iii) Describe a mechanism that is consistent with your rate equation, and indicate which step
in the mechanism is the rate determining step. Explain your reasoning.
(iv) Hence suggest why propanal, CH
3
CH
2
CHO, reacts with HCN at a faster rate than does
propanone.
(v) State the roles of HCN and NaCN in the mechanism of this reaction.
[10]
UCLES &MOE 2007 9746/03/0/N/07
9
(c) The reaction between propanal and HeN produces an equimolar mixture of two isomers
D and E. When the v ~ p o u r of either isomer is passed over hot aluminium oxide, the same
mixture of two cyanoalkene isomers F and G is produced.
Describe the types of isomerism shown here.
Explain why each of the two isomers D and E produce the same mixture of
cyanoalkenes.
You should include the displayed formulae of all the compounds D - G in your answer. [5]
[Total: 20]
UCLES & MOE 2007 9746/03/0/N/07 [Turn over
10
5 (a) (i) Describe the requirements needed for two molecules to form a hydrogen bond between
them, illustrating your answer with a suitable example.
(ii) The first four members of the series of carboxylic acids represented by the general
formula H-(CH2)n-C02H (n =0, 1, 2, 3...) are fully soluble in water, but as the value of n
increases from 4 upwards, the acids become increasingly insoluble.
By considering the relevant interactions between the molecules of the carboxylic acids
with each other, and also with the solvent, suggest reasons for this decreasing solubility.
[6]
(b) Human serum albumin, HSA, is an important protein that transports long chain fatty acids
and other hydrophobic molecules in the bloodstream. The HSA molecule is a single chain of
570 amino acids, 67% of which are incorporated into an a-helix. It is a globular protein and
takes up a roughly spherical shape in water.
Eight of the most common amino acids in the HSA molecule are listed below.
formula of side chain
number of amino
amino acid
(R in RCH(NH
2
)C0
2
H)
acids residues per
molecule of HSA
glutamic acid -CH
2
CH
2
C0
2
H 80
leucine -CH
2
CH(CH
3
)2 58
lysine
-CH2CH2CH2CH2NH2
58
valine -CH(CH
3
)2 45
cysteine -CH
2
SH 36
phenylalanine -CH
2
C
s
H
s
33
threonine -CH(OH)CH
3
27
serine -CH
2
OH 22
(i) What is understood by the term primary structure of a protein?
(ii) Use three of the above amino acids to construct the displayed formula of a possible
section of the protein chain of HSA.
(iii) Describe how a polypeptide chain is held in the shape of an a-helix.
(iv) The cysteine residues in the HSA molecule can form disulphide bridges.
Illustrate this process by means of a chemical equation.
Assuming all the disulphide bridges are intramolecular, how many bridges could be made
within each HSA molecule?
UCLES & MOE 2007 9746/03/0/N/07
11
(v) The roughly spherical shape of the HSA molecule is due to the attractions between the
various side chains. Apart from the disulphide interaction mentioned in part (iv), describe
two other types of side-chain interaction, illustrating your answer with suitable pairs of
amino acids from the table above.
(vi) Long chain fatty acids such as stearic acid (n = 17 in the general formula in part (a)(ii)
are carried through the bloodstream in the inside of the HSA molecule. Suggest two
amino acids in the above table which would interact with the long chain on stearic acid.
(vii) The amino acids whose side chains are on the outside of the HSA molecule are likely
to interact strongly with water molecules. Suggest three amino acids in the above table
which are likely to do this.
[14]
[Total: 20]
UCLES & MOE 2007 9746/03/0/N/07
12
BLANK PAGE
Permission to reproduce items where third-party owned material protected by copyright Is Included has been sought and cleared where possible. Every
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.
9746/03/0/N/07