These answers are prepared by Catholic Junior College Chemistry Department.

No parts of this may be reproduced in any form or by any means without the prior permission of the College.

2013 A Level Paper 2 Suggested Solutions and Comments

Question 1 – Planning (P)

Use what you know of volumetric chemistry and formation of complex ions to answer the
question. Not expected to have prior knowledge of the use of spectrometer.

(a) [Cu(H2O)6]2+ + 4 NH3 → [Cu(NH3)4]2+ + 6 H2O

(b) colour: orange

explanation: [Cu(NH3)4]2+ is deep blue in colour. The complementary colour, which is
the colour absorbed, is orange.
R O
Use the colour wheel to help you determine the complementary colour.
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(c) In unfamiliar contexts, required elements of the plan will be specified. Y
Must describe how to use the appropriate apparatus for each step! B G

Preparation of standard solution of copper(II) sulfate:

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1. Weigh a dry, empty weighing bottle and record its mass as m1.

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2. Accurately place 124.8 g of hydrated copper(II) sulfate in the weighing bottle and
reweigh. Record the mass as m2.

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3. The mass of hydrated copper(II) sulfate used in preparation of the standard
solution is calculated as (m2 - m1) g.

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4. Transfer the hydrated copper(II) sulfate and washings to a 250 cm3 beaker and

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add distilled water. Stir the mixture with a glass rod to dissolve the solid.
5. Transfer the solution and washings to a 250 cm3 volumetric flask. Top up to the
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mark with distilled water, shake the flask to homogenise the solution and leave to
stand.
Need to weigh and record empty, filled and residue masses!
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Preparation of range of diluted solutions:

1. Fill a burette (A) with the standard solution prepared above, and another burette
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(B) with distilled water.

2. Dispense the following volumes from each burette into separate conical flasks:

Flask Volume from Volume from

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no. burette A / cm3 burette B / cm3

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1 20.00 0
2 17.50 2.50
3 12.50 7.50
4 10.00 10.00
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5 7.50 12.50
6 5.00 15.00
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The concentrations in flasks no. 1-6 are 2.00, 1.75, 1.25, 1.00, 0.75 and 0.50 mol
dm-3 respectively.
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Do not use measuring cylinder! Pipette, burette, volumetric flask are all okay.

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 Preparation of the copper-ammonia complex:
1. Using a 100 cm3 pipette, add 100 cm3 of aqueous ammonia to each of the flasks
no. 1-6.

Obtaining the calibration curve:

1. Place a few cm3 of solution from flask no. 1 inside the spectrometer and record
the absorbance.
2. Repeat step 1 for flasks no. 2-6, and use the results to plot the calibration curve:

absorbance
x
x
x
x
x
x
0 0.50 0.75 1.00 1.25 1.75 2.00 concentration / mol dm -3
Line must be straight and pass through origin.

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Determination of the concentration of copper(II) sulfate in solution X:

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1. Using a 20 cm3 pipette, pipette out 20 cm3 of solution X into a conical flask.

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2. Using a 100 cm3 pipette, add 100 cm3 of aqueous ammonia to the flask.

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3. Measure and record the absorbance as in step 1 of the above part.

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4. Read off from the calibration curve the concentration of copper(II) sulfate from
the corresponding absorbance.
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Justification:
Mass of hydrated copper(II) sulfate:
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No. of moles of copper(II) sulfate in 250 cm3 solution = (250/1000) x 2.00 = 0.500 mol
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Mr of hydrated copper(II) sulfate = 63.5 + 32.1 + 4(16.0) + 5[(16.0) + 2(1.0)] = 249.6

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Don't forget to count in the water of crystallisation!

Mass of hydrated copper(II) sulfate required = 249.6 x 0.500 = 124.8 g

Volume of aqueous ammonia:

From (a), 1 mol [Cu(H2O)6]2+ reacts with 4 mol NH3.
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For NH3 to be in excess for flask no. 1 (2.00 mol dm-3),

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at least 4 x 20 = 80 cm3 of aqueous ammonia (also 2 mol dm-3) to be added.

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Question 2 – Data-based
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(a)(i) Reaction (1). This is because the enthalpy change of this reaction is the most
exothermic.

(a)(ii) In reactions (2) and (4), there is an increase in the number of moles of gas, from 1
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mol to 2 mol in (2) and none to 1 mol in (4). This results in a significant increase in
the level of disorder in the system. However, there is no increase in the number of
moles of gas for the other three reactions.

Answer specific to reactions (2) and (4). Must mention change in no. of moles of gas,
not just increase in gaseous products.

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 (a)(iii) ∆G = ∆H – T∆S
= – 24.8 – (298 + 500)(15.8/1000)
= – 37.4 kJ mol-1
Remember to convert temperature to Kelvins and entropy change to kJ mol-1 K-1.
As T increases, – T∆S becomes more negative, so ∆G becomes more negative.
Spontaneity increasing with increasing temperature.

(a)(iv) Le Chatelier’s Principle states that when a change is made to a system at equilibrium,
the system will act to oppose the change.
Reaction (2): C (s) + CO2 (g) ⇌ 2 CO (g) ∆H > 0
As T increases, position of equilibrium should shift to the right to increase pCO
because the forward reaction is endothermic. However, as pressure increases,
position of equilibrium should shift to the left to reduce the increased pressure, thus
decreasing pCO since there are more moles of gas on the left. The two effects cancel
out, hence there is no change in the partial pressure of CO.

Need to state effect of each change on pCO. Conclusion depends on reasoning. Not
expected to know whether they will cancel out, or which change has a greater effect.

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(a)(v) Mass of SiO2 in one tonne = (3.5/100) x 1 x 106 = 35 000 g

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Mr of SiO2 = 28.1 + 2(16.0) = 60.1

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No. of moles of SiO2 = (35 000/60.1)
= 582.4 = No. of moles of CaCO3

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Mr of CaCO3 = 40.1 + 12.0 + 3(16.0) = 100.1
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No. of moles of CaCO3 = 582.4 x 100.1 = 58 300 g
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Because %mass of silicon dioxide was given to 2 s.f., answer cannot be more than 3
s.f.!
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(b)(i) Fe3+ + Sn2+ → Fe2+ + Sn4+

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(b)(ii) Fe3+ + e- ⇌ Fe2+ Eo = + 0.77 V

Sn4+ + e- ⇌ Sn2+ Eo = +0.15 V
Eocell = +0.77 – (+0.15) = +0.62 V
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(b)(iii) Fe2+ + 2 e- ⇌ Fe
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Eo = - 0.44 V
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E cell = - 0.44 – (+0.15) = - 0.59 V

While Eocell for the reduction of Fe3+ to Fe2+ by Sn2+ is positive and hence feasible,
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Eocell for the reduction of Fe2+ to Fe by Sn2+ is negative and hence not feasible.
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Note that while you could also consider the possibility of Cl- acting as a reducing
agent, this is not obviously the focus of the question.
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 (c)(i)
titration number 1 2 3
titre / cm3 21.85 21.40 21.50

Results chosen should be consistent (within 0.10 cm3).

Average titre = (21.40 + 21.50)/2 = 21.45 cm3

Number of moles of Cr2O72- required = (21.45/1000) x 0.100
= 2.15 x 10-3 mol

(c)(ii) Cr2O72- + 6 Fe2+ + 14 H+ → 2 Cr3+ + 6 Fe3+ + 7 H2O

Retrieve the relevant half-equations from the Data Booklet and balance.

(c)(iii) No. of moles of Fe2+ in 25.0 cm3 of solution = 6 x 2.15 x 10-3 = 0.0129
Based on the mole ratio in (ii)
No. of moles of Fe2+ in 250.0 cm3 of solution = 0.129

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Don’t forget this step!

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Mass of Fe in 11.15 g of ore = 0.129 x 55.8 = 7.18 g

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%mass of Fe in 11.15 g of ore = (7.18/11.15) x 100 % = 64.4 %

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Question 3
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(a)(i) reagent A: Na or NaOH

Na2CO3 and NaHCO3 are not accepted as phenol is too weak an acid to react with
them.
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reagent B: (CH3)2CHCOCl

Cannot use the carboxylic acid as phenol is too weak a nucleophile to react with it.

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 (a)(ii)

(a)(iii) Reddish-brown bromine is decolorised and a white precipitate is seen.

While HBr is formed, the amount formed from a small amount of aq. Br2 will not be
visible as steamy fumes, and will most likely dissolve in the small amount of water
present from the aq. Br2.

(b)(i)

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Equation must be balanced.

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(c)(i) The –OH group in phenols is attached to an electron-withdrawing benzene ring,

polarizing the O-H bond to a greater extent. However, the –OH group in alcohols is
attached to an electron-donating alkyl group, thus the O-H bond is polarized to a
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smaller extent. As a result, it is easier for the O-H bond in phenols to break and
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release H+ than that in alcohols, hence phenols are more acidic.

OR
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Negative charge on the phenoxide ion is delocalised into the benzene ring, thus
dispersing it. Negative charge on the ethoxide ion is intensified by the electron-
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donating alkyl group. Thus phenoxide ion is more stable towards recombination with
H+ than ethoxide ion, hence phenols are more acidic.

(c)(ii) Ka = 10-7.4 = 3.98 x 10-8 mol dm-3

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[H+] = 0.001 x 3.98 x 10-8 = 6.31 x 10-6 mol dm-3

pH = - lg (6.31 x 10-6) = 5.20

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 (c)(iii)

The bond angles around the C=C carbons must be drawn accurately, i.e., NOT like this:

Question 4

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(a) The nuclear charges of iron and copper are greater than that of calcium, however,
there is little to no increase in the shielding effect provided by the 3d electrons in iron

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and copper. Thus the attraction by the nucleus for the outermost electrons is greater

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and they have smaller atomic radii.

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Both nuclear charge and shielding effect need to be addressed in this answer.
(a)(ii) Observe that density = mass/volume
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Since the relative atomic masses of iron and copper are greater than that of calcium,
and the atomic radii of iron and copper are smaller than that of calcium, therefore the
densities of iron and copper are significantly greater than that of calcium.
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Structure: Calcium has a giant metallic structure with a lattice of Ca2+ ions in a sea of
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(b)(i)
delocalised electrons.
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Bonding: Ca2+ ions and electrons are attracted to each other by electrostatic forces of
attraction (metallic bonding)
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Vague: “free electrons”, “sea of electrons”; should mention the word “delocalised”
Vague: “electrostatic attraction” without specifying the particles involved.
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(b)(ii) Fe2+ has a higher charge density than Ca2+ due to its smaller ionic radius. Also, 3d
and 4s electrons in iron can contribute to the sea of delocalised electrons, thus iron
has a significantly higher melting point than that of calcium.
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(c)(i) Due to its high density, copper wires are heavy and tend to sag.

Application to real-life situation.

(c)(ii) Cu 1s22s22p6 3s23p63d104s1

Cu2+ 1s22s22p6 3s23p63d9

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 (c)(iii) Impure copper is purified via electrolysis, with impure copper at the anode and pure
copper at the cathode, and copper (II) sulfate solution as the electrolyte, and a
current passed through the solution.
Copper at the anode is oxidised and goes into solution as Cu2+, which is then
reduced and deposited at the cathode as pure copper. Impurity metals are either not
oxidised and drop to the bottom as anode sludge, or are not reduced at the cathode
and remain in solution.

Electrolysis method and electrolyte used need to be specified. But note the no. of
lines given and do not over-write! This part (iii) is 3 marks at most!

(d)(i) Ca(NO3)2 → CaO + 2NO2 + ½ O2

Check that your equation is balanced.

(d)(ii) Cu2+ has a smaller ionic radius than Ca2+, hence it has larger polarising power and is
able to polarise the NO3- ion to a greater extent. Hence copper (II) nitrate will require

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less energy and thus a lower temperature to decompose.

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Ensure that you are referring to ionic and not atomic radius, and the metal ions and

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not the atoms!

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Question 5

(a) Enzymes, structure (to provide support), transport, defence (antibodies) (any three)
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Note that it is the function that is asked for in this question. Question did not ask to
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name the protein (e.g., haemoglobin).

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(b)(i) cys-tyr-ile-gln-asn-cys-pro-leu-gly

Don’t be tricked by the disulfide linkage at cys – follow the amide linkages.
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(b)(ii)
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The question hints that there might be more than one functional group that can be
ionised. So either the amine group at the N terminus at cys or the phenol group on tyr
can be chosen as the answer.

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 (c) Tertiary structure.
Tertiary structure of oxytocin is maintained through R-group interactions such as
disulphide linkages between the R-groups of two cys (-SH), hydrogen bonds between
the R-groups of gln and asn, van der Waals forces between the R-groups of leu and
ile, and ionic bonds between the deprotonated R-group of tyr (-O-) and the protonated
amine end of oxytocin at cys (-NH3+).

(d) Hg2+ can break the disulfide linkages between cys R-groups and form bonds with
them, and it can also form ionic bonds with charged R-groups, thus disrupting the
original ionic bonding within the protein. Both effects disrupt the tertiary structure of
the protein and result in denaturation of the protein.

(e)(i) Hydrolysis

Note that the reagent and conditions stated allow for complete hydrolysis of the
protein, where all the amide bonds are hydrolysed.

(e)(ii)
H 3N

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HO C

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O O
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H 3N
OH
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HO O
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Due to the acidic conditions, all amine groups are protonated. Amide bond on side
chain of gln is also hydrolysed, but note that the NH4+ end is not considered an
organic product.
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(f)
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Free radical is a species with an unpaired electron.

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Not “single” or “lone” electron!

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The O-O bond in hydrogen peroxide breaks homolytically, with one electron in the
bond going to each O atom to form two •OH free radicals.
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