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CHEMISTRY
9647/03
October/November 2010
2 hours
Answer Paper
Data Booklet
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UNIVERSITY of CAMBRIDGE
International Examinations
DC (N F/SHW) 33440
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2
Answer any four questions.
(a) (i)
(ii)
1/ 1 (s)
3 2
--7
2/
3
ICZ 3 (1)
[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)
(ii)
(iii)
[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~------~}
NaOH in ethanol
heat
..
..
NaOH in ethanol
heat
..
[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many applications they have now been replaced by alkanes.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]
9647/03/0/N/10
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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.
9647103/0 /N/10
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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]
9647103/0/N/10
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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.
(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]
(ii)
(iii)
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)
(iv)
[8]
[Total: 20]
9647/03/0/N/1 0
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[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)
(ii)
(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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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)
(ii)
By selecting appropriate EB- values from the Data Booklet, explain why it would be
expected that this redox reaction would not occur.
(iii)
[4]
(f)
An alkaline solution of complexed Cu 2+(aq) is used in organic chemistry to test for a particular
functional group.
(i)
(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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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.
9647/03/0/N/1 0