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SECTION B
1 (a) Alkanes are relatively unreactive. Explain.
[1]
• Alkanes are relatively unreactive because the C-H and C-C bonds are non-polar due to
the similarity in electronegativities and hence unreactive towards polar solvents.
Or
the C-H and C-C bonds have high bond energies which makes it difficult to break.

(b) Alkanes are commonly used as fuels. Four identical vehicle models with different fuels were
tested for fuel consumption. The fuel consumption and carbon dioxide emissions per litre of fuel
burnt are shown below.

Vehicle Fuel Fuel CO2 produced

consumption
(g CO2/L of fuel)
(L/100 km)

1 LPG (liquefied petroleum gas) 19.7 1665

2 Petrol (unleaded, 91 octane) 14.5 2392

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3 E10 (petrol with 10% ethanol) 14.2 2304

4 Petrodiesel 9.2 2640

(i) The energy content of a fuel is the heat energy obtained when a certain quantity of the
fuel is burnt. Deduce which fuel has the highest energy content.
[1]
• Petrodiesel has the highest energy content as the vehicle requires the least fuel
to travel the same distance of 100 km

OR 1L of petrodiesel enable the vehicle to travel the longest distance.

Note: cannot deduce based on CO2 produced

(ii) A company claimed that E10 (petrol with 10% ethanol) is more environmentally friendly
than Petrol (unleaded, 91 octane) as E10 produces less mass of CO2 per 100 km.
Determine if the claim is true.
[1]
Yes, the claim is true.
Mass of CO2 produced per 100 km

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= fuel consumption (L/100 km) × mass of CO2 produced per L of fuel

Fuel Mass of CO2 produced per 100 km

E10 14.2 x 2304 = 3.27 x 104 g

Petrol (unleaded, 91 octane) 14.5 x 2392 = 3.47 x 104 g

• Answer with reasoning

(iii) Besides carbon dioxide emission, there are also other pollutants from car exhaust such
as oxides of nitrogen. Vehicles are fitted with catalytic converters to reduce such
pollution.
Write an equation to show how the catalytic converter removes nitric oxide, NO, via its
reaction with carbon monoxide.
[1]
• 2NO + 2CO → N2 + 2CO2
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(c) A vehicle that is powered by a diesel engine is able to use either petrodiesel or biodiesel as a

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fuel. One example of biodiesel is methyl palmitate, C17H34O2 (Mr = 270).

(i) Write an equation which describes the standard enthalpy change of combustion, ΔHcO,
of solid methyl palmitate.
[1]
𝟒𝟗
• C17H34O2(s) + O2(g) → 17CO2(g) + 17H2O(l)
𝟐

Note: must be 1 mole of methyl palmitate, must include all correct state symbols

(ii) 2.28 g of methyl palmitate was burnt in excess oxygen in a bomb calorimeter and the
temperature rise of 300 g of water was found to be 7.5 oC.
Given that the standard enthalpy change of combustion of methyl palmitate is 5.91 x 103
kJ mol-1, determine the heat capacity of the calorimeter in kJ/oC.
[2]
• Heat released by the combustion of 2.28 g of methyl palmitate
𝟐.𝟐𝟖
= x 5.91 x 103
𝟐𝟕𝟎

= 49.9 kJ
Heat absorbed by the calorimeter and water
= C∆T + mc∆T
= C(7.5) + 300 x 4.18 x 7.5

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• C = [49.9 x 103 – (300 x 4.18 x 7.5)]/7.5

= 5.40 kJ/oC

(d) Catalytic reforming is a chemical process used to convert petroleum refinery naphthas into high-
octane liquid products called reformates. These reformates can be converted into compounds
with benzene rings.
An example of reforming n-octane to 1,2-xylene is shown below:

Pt and Al2O3
(l) (l) + 4H2(g)
500OC, 20 atm

n-octane 1,2-xylene

(i) Using values in the Data Booklet, calculate the enthalpy change of the above reaction.
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[2]

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Bond broken Bonds formed

7C-C 2C–C

18 C – H 6C C

10 C – H

4H–H

• ∆Hr = 7(+350) + 18(+410) – [2(+350) + 6(+520) + 10(+410) + 4(+436)]

= (+9830) – (+9664)
• = +166 kJ mol-1
Note: Bond Breaking is endothermic (positive). For the benzene ring, use bond energy
+520 kJmol-1

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(ii) Using appropriate data from the table below, construct a suitable cycle to calculate the
standard enthalpy change of the reaction that converts n-octane to 1,2-xylene.

Standard enthalpy change of formation of n-octane -248.5 kJ mol−1

Standard enthalpy change of formation of 1,2-xylene -24.4 kJ mol−1

Standard enthalpy change of combustion of hydrogen -286 kJ mol−1

[2]
• Energy cycle
CH3 CH3

CH3
CH 2
CH 2
∆HrO CH3
CH 2
(l) (l) + 4H 2 (g)

CH 2 CH 2
CH 2

-248.5 -24.4

8C(s) + 9H2(g)
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By Hess’ Law,
∆HrO + (-248.5) = -24.4
• ∆HrO = +224 kJ mol-1

Note: ∆HcOof hydrogen is not required. State symbols needs to be included in the
energy cycle

(e) There are 2 other positional isomers of 1,2-xylene.

Suggest which of the isomer is less likely to be formed along with 1,2-xylene when it is
synthesised from methylbenzene. Explain your answer.
[1]
• In the synthesis of 1,2-xylene from methylbenzene,–CH3 is 2,4-directing, 1,3-xylene
is less likely to be formed along with 1,2-xylene.

[Total: 12]

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2 (a) Tripeptide-1 is a synthetic signal peptide known to work with copper in skin to visibly repair
cells that have begun to deteriorate due to age and sun exposure.
It is made up of glycine, lysine and histidine. Some information of these amino acids are as
follows:

amino formula of R group pKa of R pKa of α- pKa of α-

acid (in RCH(NH2)CO2H) group carboxyl group ammonium ion
glycine ─H - 2.34 9.60
lysine ─CH2CH2CH2CH2NH2 10.53 2.18 8.95
histidine 6.00 1.82 9.17
1

─CH2 2

(i) The two nitrogen atoms in the R group of histidine have the same hybridization. By
considering positions of the orbitals occupied by the lone pairs of N1 and N2, explain why
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N2 is basic while N1 is not basic.
[2]
• N2 is basic as the lone pair of electrons is in the sp2 hybrid orbital which is on the
plane and hence available for dative bonding with a proton.
• The lone pair of electrons on N1 is in the p orbital and can delocalise with the
double bonds in the ring, resulting in it being not available for dative bonding with
a proton and not basic.

(ii) Given that Tripeptide-1 has the sequence of glycine-histidine-lysine, draw its structural
formula.
[1]

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Note : the aminoacids are linked by using the α-amino gp and not the amino gp from the
–R group.

(iii) Using your answer in (a)(ii), show the ionic form which Tripeptide-1 would exist at
pH = 8.
[2]

•• based on protonation and deprotonation of the different groups

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ECF based on the (a)(ii)

(b) Dopamine functions as a neurotransmitter.

dopamine
Suggest the structure of the product formed when dopamine reacts with concentrated nitric
acid at room temperature and pressure.
[1]

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NO2

+
NH3

NO2

NO2
•

Note:
- Check for multiple reactions.
- When concentrated HNO3 is used, substitution at 2- and 4- positions wrt to –OH in phenol
occur if it is not already occupied. If dilute HNO3 is used, there is only mono-nitration.
- When there is more than 1 -OH on the benzene ring, check if electrophilic substitution can
occur wrt each –OH.
(c) Further metabolic action of dopamine produces epinephrine which has a similar structure to
Compound W.
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Compound W
Compound W exhibits stereoisomerism. State the number of stereoisomers and draw a pair of
enantiomers. [2]

• No. of stereoisomers = 22 = 4
• Either pair of enantiomers

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* *

* *
(CH3 )2N N(CH3)2

mirror plane

Or
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* *

* *
N(CH3)2
(CH3)2 N

mirror plane

Note: Need to show 3D around each chiral center.

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3 Copper is a transition element with many uses. Its name is derived from the Old English name
'coper', which originates from Cyprus, from where the element gets its name.

(a) A student used the following setup to purify copper using aqueous copper (II) sulfate solution.

(i) Using relevant data from the Data Booklet, predict the type of redox reaction that occurs
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at each electrode A and B.
[1]
Note: The 2 half-cells on the left acts as an galvanic cell (i.e. the battery for the electrolytic
purification of copper on the right)

Since EoFe3+/ Fe2+ (+0.77V) is more positive than EoZn2+/Zn(-0.76V),

Fe3+ undergoes reduction: Fe3+ + e- → Fe2+ (graphite electrode is the positive terminal)

Zn undergoes oxidation: Zn → Zn2+ + 2e- (Zn electrode is the negative terminal).

Electrode B is connected to the negative terminal of the galvanic cell, hence gaining
electrons, reduction taking place.

Electrode A is connected to the positive terminal of the galvanic cell, hence losing
electrons, oxidation taking place.

Electrode A: oxidation
Electrode B: reduction

(●both electrode A&B)

(ii) State at which electrode A or B should the impure copper be placed in this electrolytic
set-up.
[1]
Electrode: ● A

Note: The impure copper is to be placed at the anode. Pure copper at the cathode.

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(iii) An alloy of copper, composed mainly of copper, with aluminium and silver as minor
impurities, was purified in the electrolytic set-up in (a).

Explain, with reference to relevant Eo values, what happens to the aluminium and silver
impurities during this purification procedure.
[3]
From the Data Booklet:
Ag+ + e-  Ag Eᶿ = +0.80 V
Cu2+ + 2e-  Cu Eᶿ = +0.34 V
Al3+ + 3e-  Al Eᶿ = -1.66 V
• Al would be more readily oxidised than Cu because Eᶿ(Al3+/Al) is more negative
than Eᶿ(Cu2+/Cu), thus, Al would be oxidized together with Cu, producing Al3+ at
the anode.
• Al3+ ions remain in the electrolyte solution, and will not be reduced at the
cathode since Eᶿ(Al3+/Al) is more negative than Eᶿ(Cu2+/Cu), and have a lower
tendency to be reduced than Cu2+ ions.
• Silver (Ag), however, will not be oxidised as Eᶿ(Ag+/Ag) is more positive than
Eᶿ(Cu2+/Cu). Silver will be deposited below the anode as ‘anode mud.

Note: the electrode potential of the impurities are to be compared to electrode potential
of copper. The electrode potential are not to be ranked from most negative to least
negative to decide which element are to be oxidized.
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(b) Copper is a transition element that forms a rich variety of compounds with varying oxidation
states.

(i) Suggest the formulae of Compound A and C, as well as the complex ions in B and D.
[2]
Compound A: Cu(OH)2

Complex ion B: [Cu(NH3)4(H2O)2]2+

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Compound C: Cu2I2 or CuI

Complex ion D: [CuCl4]2–

(ii) Write a balanced equation for the formation of E.

[1]

Equation: Cu2+ + Cu + 4HCl → 2[CuCl2]– + 4H+

Note: Students need to be familiar with the formulaes of copper-containing complexes.

Common errors include: [Cu(NH3)4(OH)2]2+; [Cu(NH3)2(H2O)4]2+; CuI2 as copper (I)
iodide.

(c) Copper forms a very useful group of organic compounds known as Gilman reagents.

2CH3Li + CuI → (CH3)2CuLi + LiI

Gilman reagent

Gilman reagents can react with acyl chlorides to form ketones. An example is shown below:
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(i) Gilman reagent, (CH3)2CuLi, may be assumed to be a CH3– nucleophile. The mechanism
for this reaction proceeds as follows:

1. The CH3– anion, which acts as a nucleophile, attacks the electron deficient carbon
atom in the benzoyl chloride, and the π bond will break.

2. In the next step, the π-bond will re-form, giving the final ketone.

Draw diagrams to illustrate the mechanism for the reaction. Show relevant lone pairs
and dipoles and use curly arrows to indicate the movement of electron pairs.
[2]

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slow

fast

●●
1m for each step

A student proposed the following synthetic route to produce vanillin, the active molecule that
gives the sweet smell from vanilla extract.
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(ii) State the reagent and condition for Step 1.
[1]
●Acidified K2Cr2O7, heat under reflux
Or Acidified KMnO4, heat under reflux

(iii) Describe a chemical test to confirm that vanillin is produced successfully via this
synthetic route.
[2]

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●Test: 2,4-DNPH, rtp

●Observation: orange ppt formed if vanillin is produced
OR
●Test: Aqueous alkaline iodine, warm
●Observation: yellow ppt formed if vanillin is produced
[Total: 13]

4 PbBr2 is a sparingly soluble salt.

PbBr2(s) ⇌ Pb2+(aq) + 2Br−(aq)
Ksp of PbBr2 is 6.60 x 10-6 mol3dm-9 at 25˚C

(a) Calculate the maximum mass of PbBr2 that can dissolve in 500 cm3 of water at 25˚C.
[2]
2+ −
PbBr2(s) ⇌ Pb (aq) + 2Br (aq)
x x 2x
2+ - 2
Ksp = [Pb ][Br ]
6.60 x 10-6 = (x)(2x)2
●x = 0.0118 moldm-3
Amount of PbBr2 in 500cm3 of water = 500/1000 x 0.0118 = 5.91 x 10-3 mol
●Mass of PbBr2 = 5.91 x 10-3 x (207.2 + 2(79.9)) = 2.17g
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(b) At a constant temperature of 25 ˚C, the following graphs show the mass of PbBr2
dissolved and solubility product of PbBr2 against time.

At time t1, aqueous silver nitrate was added to the saturated solution of lead bromide. On
the following graphs, sketch how the two graphs would look like from time t 1 to t2, when a
new equilibrium has reached. Explain your answer.
[3]

 correct line

Presence of Ag+ in the solution will precipitate AgBr (s) as a cream ppt, hence
[Br-] decreases.

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By Le-Chatelier’s Principle (LCP), position of equilibrium will shift right to increase

the concentration of [Br-]. Solubility of PbBr2 increases (graph shows an increase
reaching new eqm.

 correct line

Ksp remain constant as it is only affected by temperature.

Every 2 = 1m

Common error: Commenting that [Pb2+] will be lower due to formation of Pb(NO3)2 which
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is soluble and does not affect [Pb2+].

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(c) The plot of PV/RT against P for one mole of bromine gas from the electrolysis of molten
lead bromide at 646K is given below.

Br2 (350K)

(i) Show, on the same axes, how one mole of Br2 (g) will behave at 350K.
[1]
(ii) With reference to your answer in (c)(i), explain the shape of the graph when
bromine gas is cooled to 350K.
[1]

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●At a lower temperature of 350K, bromine molecules will possess less kinetic
energy and move slower. Inter-molecular forces of attraction (Instantaneous-
dipole-induced dipoles interactions) between bromine molecules become more
significant, hence deviate even more (greater negative deviation).

Common error: Commenting that intermolecular forces of attraction being “stronger”

instead of “more significant”.
[Total: 7]
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