3(a) Iron metal has traditionally been extracted from its ore using a Blast furnace.

The process uses coke (carbon) and haematite (Fe2O3) in three stages,
whereby

 coke is first oxidised by air to form carbon dioxide;
 the carbon dioxide formed further reacts with more coke to form carbon
monoxide;
 the haematite is reduced to obtain the iron metal

New research proposes that iron could be recovered via electrolysis. This
involves passing current via inert platinum electrodes into a mixture of molten
Fe2O3. This new process is thought to be more advantageous than using the
current Blast furnace method.

(i) Draw a diagram to illustrate the electrolysis set-up, showing clearly the
polarity of the electrodes and the species attracted to and formed at each
electrode.

(ii) Give the equations, including state symbols, for the reactions occurring
at each electrode.

(iii) An initial pilot production plant using the new method yields 5 kg of iron
per day. Calculate the current to be supplied per day if the pilot plant
runs continuously for 24 hours each day.

(iv) Construct the equations for the reactions occurring at each stage of the
Blast furnace extraction of iron.

(v) Suggest an advantage of the new electrolysis method over the Blast
furnace method.
[8]

(b) Solutions of iron(II) compounds are commonly prepared in the laboratory.

(i) By selecting two appropriate half-equations from the Data Booklet,
explain why iron(II) solutions are normally made up and stored in the
presence of acids instead of bases.

(ii) With the aid of suitable equations, explain why iron(II) solutions can
catalyse the reaction involving iodide ions with peroxodisulfate(VI) ions.

2I (aq) + S2O82 (aq)  I2 (aq) + 2SO42 (aq)
[5]
(c) Iron compounds can be used to catalyse a number of organic reactions. One
such organic reaction is the Michael reaction as shown below.

The reaction can also be carried out using sodium ethoxide (CH3CH2O-Na+) as
a catalyst, whereby the labelled hydrogen H reacts with the ethoxide ion as a
proton and is eventually transferred to its new position on the product.

(i) Explain how the ethoxide ion is able to remove the proton in the Michael
reaction.

(ii) State the type of reaction which occurs in the Michael reaction.

The Michael reaction can be used to synthesise a useful blood anticoagulant
known as Warfarin. The synthesis of Warfarin can give rise to two possible
isomers.

(iii) Suggest the structure of compound A used to form Warfarin.

(iv) State the type of isomerism present in Warfarin and sketch the structures
of these two isomers. [You may use R to represent a part of the molecule
in your answer]

(v) Draw the structure of the product formed when 2,4-DNPH is reacted with
Warfarin.

[7]
[Total: 20]
4 Oxygen reacts with various Period III elements to produce compounds of
numerous uses. Examples are Al2O3 which is often used as a refractory
material and chlorine oxides which act as oxidising agents used in water
treatments and in bleaching.

(a) Element X forms a white oxide that is soluble in cold water. Its chloride
dissolves in water to form a neutral solution.

Element Y forms two oxides. 0.09 mol of one of the two oxides produces 12.3
g of white precipitate when shaken with excess calcium hydroxide solution. A
solution containing 1 mol of the oxide of element Y forms a neutral solution
when the same amount of the oxide of element X is added to it.

Given that X and Y are Period III elements, identify the element X and the oxide
of Y in the above reactions. Explain the observations with the help of relevant
equations.
[4]

(b) When a sample of an oxide of chlorine, ClmOn, was vapourised in a suitable
apparatus at 250 oC and 101 kPa, the density of the gas was found to be 1.60
g dm-3.

(i) Calculate the molar mass of the gas and hence suggest the value of m
and n.

(ii) Explain why the molar mass obtained in (b)(i) is different from the
theoretical value.
[4]

(c) A to F are consecutive elements having atomic numbers between 10 to 20.

(i) Write an equation that represents the third ionisation energy of
aluminium.

(ii) From the graph below, identify which element, A to F, is aluminium.
Explain your answer.

3rd I.E. / B
kJ mol -1 A
l
2
O D F
E
3
A C
a
t atomic number
A
[3]
(d) Other than its use as a refractory material, Al2O3 is also used in chemical
reactions involving organic compounds. In the reaction scheme below, Al2O3
is used to dehydrate chloramphenicol-X to form compound D.

A B+C
CH3COCl hot alkaline
KMnO4
chloramphenicol-X

Al2O3 Step I

D
Step II

(i) Identify the lettered compounds A to D.

(ii) Suggest the reagent and condition used in step II. State the type of
reaction occurring in step II.

(iii) Describe a simple chemical test to distinguish between chloramphenicol-
X and its isomer shown below.

[9]
[Total: 20]
5 Fluoxetine is an anti-depressant drug or mood elevator commonly used to treat
depression and other mental illness like obsessive compulsive behaviour.

The structure of Fluoxetine is shown below:

Fluoxetine

(a) (i) Draw a diagram to show how hydrogen bonding occurs between one
molecule of Fluoxetine and two molecules of water.

(ii) Suggest why Fluoxetine is insoluble in water despite the formation of
hydrogen bonding between Fluoxetine and water molecules.

(iii) Fluoxetine is manufactured and merchandised as Fluoxetine
hydrochloride. Explain, in terms of structure and bonding, why this is
so.
[5]

(b) Bupropion is another type of anti-depressant. It is synthesised from
3-chloropropiophenone as shown in the pathway below.

O O O
Cl. Step I Cl. Br Step II Cl. NH

3-chloropropiophenone intermediate X Bupropion

(i) State the type of reaction that occurs in step I.

(ii) Suggest the reagents and conditions for step II.

(iii) Draw the structure of the product obtained by heating intermediate X
with aqueous potassium hydroxide.

[3]
(c) Compound A, C11H15NO3, has potential to treat certain mental disorders.
Compound A reacts with aqueous bromine to form compound B, C11H13NO3Br2.
1 mole of compound A reacts with 2 mole of aqueous sodium hydroxide at room
temperature. No decolourisation is observed upon heating compound A with
acidified potassium manganate(VII). Compound A reacts with iodomethane to
form compound C, C12H18NO3I, which yields a yellow precipitate with aqueous
silver nitrate at room temperature.

Suggest the structure of each lettered compound and explain the reactions
involved.
[8]

(d) In some cases of mental illness, lithium ion, Li+, can also be administered in
the form of lithium salt as a mood-stabilizing drug.

(i) Explain why Li has the lowest first ionisation energy among the Period 2
elements.

(ii) All Group I halides dissolve in water to give neutral solutions containing
hydrated ions.

Suggest why lithium forms Li(H2O)4+ ions, whereas the other Group I
halides form mainly M(H2O)6+ ions.
[4]
[Total: 20]
4 (a) Depending on the oxidation state of manganese, compounds of manganese have
various colours and they are used industrially as pigments for the colouring of ceramics
and glass.

The absorption spectrum of the compound K3[Mn(CN)6] shows a maximum at a
wavelength around 490 nm (blue-green region).

(i) State the oxidation number of manganese in this compound.

(ii) Suggest the colour of this compound.

(iii) Explain how the colour of this compound arises.
[4]

(b) Potassium manganate(VII) plays an important role in analytical chemistry.

The figures below show the standard electrode potentials, E, of various redox half
reactions. For example, in Figure 1, the line shows that the E for MnO4−/Mn2+ half-
cell is +1.52 V.

E / V E / V
Figure 1 Figure 2
−0.2 −0.2
0.0 0.0
+0.2 +0.2
+0.4 +0.4
+0.6 +0.6
+0.8 +0.8
+1.0 +1.0
+1.2 +1.2
+1.4 +1.52 V +1.4
2 2
+1.6 MnO4− Mn2+ +1.6
+1.8 +1.8
7 6 5 4 3 2 1 0 −1 −2 7 6 5 4 3 2 1 0 −1 −2
Oxidation number Oxidation number
SO42− SO32−

S2O62− S2O32− S8

S4O62−

(i) Use the lines in Figure 2 to predict what sulfur-containing species might be
formed from sodium sulfite, Na2SO3, when it is titrated with acidified potassium
manganate(VII) solution. Give a reason for your prediction.

(ii) During an actual experiment, 25.0 cm3 of 0.020 mol dm−3 acidified potassium
manganate(VII) was found to react completely with 12.5 cm3 of 0.10 mol dm−3
sodium sulfite. From these results, deduce the oxidation number of sulfur in the
sulfur-containing species at the end of the reaction.
[4]
(c) In another experiment, a solution of iron(II) sulfate was titrated against 0.020 mol dm−3
acidified potassium manganate(VII), maintaining a constant [H+] throughout the
titration. The electrode potential was measured against a standard hydrogen electrode
and the following data was obtained.

Volume of KMnO4(aq) added / cm3 E at 25 oC / V
20.0 +0.734
40.0 +0.760
60.0 +0.780
80.0 +0.806
120.0 +1.512
140.0 +1.515

The electrode potential of the mixture at 25 oC, E, is given by the expression

[Fe 3  ]
E = E (Fe3+/Fe2+) + 0.0257 ln
[Fe 2 ]

(i) Using the given expression and relevant information from the Data Booklet,
determine the value of E when [Fe2+] and [Fe3+] are equal.

(ii) Estimate the volume of KMnO4 added which corresponds to your value of E in
(c)(i).

(iii) Explain why there is a rapid increase in the value of E between 80.0 cm3 and
120 cm3 of KMnO4.

(iv) Suggest why it was necessary to maintain a constant [H+] in this experiment.
[4]

(d) Potassium manganate(VII) is used in organic chemistry in the identification of
compounds.

A compound J, C11H14, exhibits cis-trans isomerism but does not possess any chiral
carbon. Oxidation of J with hot acidified potassium manganate(VII) gives K, C9H8O3.
K reacts with aqueous alkaline iodine to give a yellow precipitate and a residual
solution. Upon acidification, the residual solution yields benzene-1,2-dicarboxylic acid:

J reacts with steam at 300 oC and 60 atm in the presence of concentrated phosphoric
acid to give L, C11H16O. L is an optically active compound which does not react with
aqueous alkaline iodine.

Deduce the structures of J, K and L based on these observations.
[8]

[Total: 20]
5 (a) Norsethite, BaxMgy(CO3)z, is a mineral consisting of barium carbonate and magnesium
carbonate. The decomposition temperatures of barium carbonate and magnesium
carbonate are 1350 °C and 540 °C respectively.

(i) Account for the difference in decomposition temperatures of barium carbonate
and magnesium carbonate.

Write equation(s) for any reaction(s) that occur on heating norsethite to 800
o
C.

(ii) A sample of pure norsethite was heated strongly at 1500 °C until no further
change occurred. The gas evolved was collected and found to occupy a volume
of 72 cm3 at room temperature and pressure. The residue was a white powder
which was dissolved in dilute nitric acid. On addition of aqueous sodium sulfate
to the resulting solution, a white precipitate of barium sulfate was formed. The
precipitate was dried and its mass was found to be 0.35 g.

Write an equation, with state symbols, to represent the decomposition of
norsethite, giving your answer in terms of x, y, and z. Hence deduce the values
of x, y and z.

[Mr of norsethite was found to be less than 300.]

(iii) In the presence of carbon, further heating of the residue would cause the
formation of carbon monoxide as a by-product.

Explain why carbon monoxide is poisonous.
[8]

(b) Explain the following observations.

(i) Iron can exhibit variable oxidation states in its compounds but calcium only
exhibits an oxidation state of +2 in all its compounds.

(ii) The melting points of iron and calcium are 1536 C and 839 C respectively.
[3]

(c) Magnesium hydroxide is sparing soluble in water. The pH of a saturated solution of
Mg(OH)2 is 10.5 at 25 oC.

Calculate

(i) the solubility of Mg(OH)2 in g dm−3 at 25 oC,

(ii) the Ksp of Mg(OH)2 at 25 oC, stating its units,
[3]
(d) Group II salts of carboxylic acids decompose to give the metal carbonate and a
carbonyl compound. For example, calcium ethanoate produced propanone.

(CH3CO2)2Ca CaCO3 + (CH3)2CO

When this reaction is carried out by heating a mixture of calcium ethanoate and
calcium methanoate, an acidic gas and a mixture of three carbonyl compounds, A, B
and C, are formed.

(i) Both A and B but not C react with Tollens’ reagent. Only A and C react with
alkaline aqueous iodine to give a yellow precipitate.

Deduce the identities of A, B and C.

(ii) A was warmed with Tollens’ reagent and the organic product formed, D, is
isolated and made to react with CH3CH2Br forming a sweet-smelling liquid,
C4H8O2.

Suggest the identity of D and name the type of reaction that D has undergone.

(iii) When B is reacted with excess hot acidified potassium manganate(VII), no
organic product remains. Explain.
[6]

[Total: 20]
Answers
3(a) (i)

(Pt cathode) (Pt anode)
– +

Fe (s) O2 (g)
formed formed

O2- (l)

Fe3+ (l)

(ii) Cathode: Fe3+ (l) + 3e  Fe (s); Anode: 2O2- (l)  O2 (g) + 4e

5  1000 I  24  60  60
(iii) = ; I = 300 A.
55.8 3  96500
(iv) C + O2  CO2 ; CO2 + C  2CO ; Fe2O3 + 3CO  2Fe + 3CO2

(v) Less / no pollutants of CO or CO2 are formed.

(b)(i) Fe(II) is stabilised with respect to Fe(III) in acidic medium compared to
basic medium. Fe2+ in acidic medium is a weaker reducing agent
compared to Fe(OH)2 in basic medium.

(ii) Fe2+ acts as a homogeneous catalyst

Step 1: 2Fe2+ + S2O82-  2SO42- + 2Fe3+

Step 2: 2Fe3+ + 2I-  2 Fe2+ + I2

(c) (i) Ethoxide ion acts as a base

(ii) (Nucleophilic) Addition

(iii)
(iv) Optical isomerism

(v)

4(a) Element X : Sodium / Na
Na2O + H2O → 2NaOH
Formula of the oxide of Element Y: SO3
Upon addition of Ca(OH)2, white ppt formed could be CaSO4
No of mol of CaSO4 = = 0.09 mol
SO3 + Ca(OH)2 → CaSO4 + H2O
white ppt

SO3 +H2O → H2SO4
H2SO4 + Na2O → Na2SO4 + H2O

(b) (i) 101 x 1000 × M = 1.60 x 103 x 8.31 × (250+273)
Molar mass of gas = 68.8 g mol-1 ≈ 67.5 g mol-1
Hence m = 1, n = 2

(ii) There is significant van der Waals forces of attraction between the ClO2
molecules.

(c) (i) Al2+ (g)  Al3+ (g) + e

(ii) C is aluminium, as it has the lowest 3rd IE. The removal of the third
electron will lead to the formation of the stable noble gas configuration
hence a small amount of energy is required to remove the valence
electron.
(i) A:

B, C:

D:

(ii) H2O (g) or steam , conc. H3PO4, 65 atm , 300C

Electrophilic Addition

(iii) Add 2,4-DNPH to each compound separately and heat.
Chloramphenicol-X will not produce orange ppt of hydrazine; its isomer
will produce orange ppt of hydrazone.

5(a) (i) Hydrogen bond
δ+
δ-
δ+
δ- δ+
δ+
δ+

δ+ δ+
δ-

δ-

(iii) Due to the presence of a large hydrophobic benzene rings.

(iii) Formation of ion-dipole interaction with water molecules causes
solvation hence drug is better is better absorbed.

(b) (i) Free radical substitution

(ii) excess (CH3)3CNH2 , heat
(iii)
(c)

A:

Or A can also be 1, 2 di-substituted isomer
:

B:

C:

(d)(i) Effective nuclear charge increases. The electrostatic force of attraction
between nucleus and valence electrons increases hence energy
required to remove the valence electrons increases.

(ii) Li+ has the smallest ionic radius among the group I metal ion.
Less H2O ligands can be datively bonded to Li+ cation, thus the
coordination number is 4 and Li(H2O)4+ ions is formed.

4 (a) (i) +3

(ii) Orange / red / yellow

(iii) In the presence of an octahedral ligand field, the degenerate d-orbitals will split
into two energy levels.
In the partially filled d-orbitals (d4) , electrons are able to promote from the
lower to the higher level by absorbing energy in the visible spectrum (blue-
green).
The colour shown is the complementary colour (orange-red or yellow).

(b) (i) SO42−

[R] MnO4− + 8H+ + 5e  Mn2+ + 4H2O E +1.52 V
[O] SO42− + 2H+ + 2e  SO32− + H2O E < +1.52 V

(ii) From the titration results,
nMnO  25.0  0.020 2
4
= = 0.4 or
n SO 2 12.5  0.10 5
3

Each mol of MnO4− accepts 5 mol of electrons when reduced to Mn2+.

This means 2 mol of MnO4− accepts 10 mol of e- from 5 mol of SO32−;
10
or each SO32− ion loses = 2 electrons.
5
Hence oxidation state of S increases by 2 units from +4 (in SO32−) to + 6 (in
SO42−)

(c) (i) [Fe 3  ]
When [Fe2+] = [Fe3+] , ln = 0.
[Fe 2 ]

Hence, E = E (Fe3+/Fe2+) = +0.77 V.

(ii) Vol of KMnO4 = 50.0 cm3

(iii) The equivalence point is reached between 80 and 120 cm3 (precisely at 100
cm3). This means that the E value switches from a calculation based on
Fe3+/Fe2+ to one based on MnO4−/Mn2+.

(iv) The E value of MnO4−/Mn2+ (and hence, the oxidizing power of MnO4−) is
dependent on [H+];
or changes in [H+] affects the value of the measured E, because of
MnO4− + 8H+ + 5e  Mn2+ + 4H2O.

(d) J K L
5 (a) (i) Mg2+ cation has a higher charge density and distorts the carbonate electron
cloud more. Hence, MgCO3 decomposes at a lower temperature than BaCO3.

MgCO3(s)  MgO(s) + CO2(g)
OR
BaxMgy(CO3)z  xBaCO3 + yMgO + yCO2

(ii) BaxMgy(CO3)z(s)  xBaO(s) + yMgO(s) + zCO2(g)

72
nCO2 = = 0.003 mol
24000

BaO(s) + 2HNO3(aq)  Ba(NO3)2(aq) + H2O(l)

Similarly, Mg(NO3)2 is also formed.

Ba(NO3)2(aq) + H2SO4(aq)  BaSO4(s) + 2HNO3(aq)

0.35
nBaSO4 = nBaO = = 0.001502 mol
(137  32.1 64)
x : z
=1 : 2

By balancing O atoms,
3z = x + y + 2z
z = x + y
x = y

 x = y = 1; z = 2

(iii) CO forms strong dative bond with Fe2+ of haemoglobin OR undergo ligand
exchange and this is an irreversible process.
Thus haemoglobin is unable to transport oxygen , causing death as the body is
deprived of oxygen.

(b) (i) Fe shows variable oxidation states due to the close similarity in energy of the 4s
and 3d electrons. Hence, once the 4s electrons are removed, some or all the 3d
electrons may also be removed without requiring much more energy.

For Ca, once the outermost electrons in the s orbitals are removed, subsequent
removal of electrons would be from the inner quantum shell which requires too
much energy.

(ii) In Ca, only 2 valence electrons are involved in metallic bonding. In Fe, both 3d
and 4s electrons are involved in metallic bonding due to their proximity in energy.
More energy required to overcome the stronger metallic bonding in Fe than in
Ca.

(c) (i) Mg(OH)2(s) Mg2+(aq) + 2OH-(aq)

pH = 10.5, pOH = 14 – 10.5 = 3.5

[OH-] = 10-3.5 = 3.162 x 10-4 mol dm-3

1
[Mg2+] = x 3.162 x 10-4 = 1.581 x 10-4 mol dm-3
2

Mr of Mg(OH)2 = 58.3

Solubility of Mg(OH)2 = [Mg(OH)2(aq)]
= [Mg2+]
=1.581 x 10-4 x 58.3 = 9.217 x 10-3 g dm-3
= 9.22 x 10-3 g dm-3

(ii) Ksp of Mg(OH)2 = [Mg2+] [OH-]2
= (1.581 × 10-4) (3.162 × 10-4)2
= 1.581 x 10-11 mol3 dm-9
= 1.58 x 10-11 mol3 dm-9

(d) (i) A and B but not C react with Tollens’ reagent  A and B are aldehydes, C is a
ketone.

A and C react with alkaline aqueous iodine to give a yellow ppt  have

group.

 A: CH3CHO; B: HCHO; C: (CH3)2CO

(ii) CH3CO2ˉ + CH3CH2Br  CH3CO2CH2CH3 + Brˉ
sweet-smelling
liquid
D: CH3CO2ˉ

Nucleophilic substitution

(iii) HCHO will be oxidised to HCO2H which is unstable and thus decomposes to
form CO2 gas and H2O.