5

9 When 25 cm3 of 1.0 mol dm–3 sodium hydroxide is completely neutralised by 1.0 mol dm–3
hydrochloric acid, the temperature of the mixture rose by 6.8 °C. What will be the temperature
change if 50 cm3 of 0.5 mol dm–3 sodium hydroxide is completely neutralised by 0.5 mol dm–3
hydrochloric acid? (Assume heat loss to be negligible in each case)

A 1.7 °C
B 3.4 °C
C 6.8 °C
D 13.6 °C

10 Potassium chloride, KCl, is commonly used as a fertilizer while potassium iodide, KI, is
frequently used as a nutritional supplement to prevent iodine deficiency.

Some thermochemical data are given in the table.

KCl(s) KI(s)
–1
standard enthalpy change of formation / kJ mol –438 –328
–1
lattice energy / kJ mol –718 –645

Which statement best describes the relative stability of Cl–(g) and I–(g)?

A Cl–(g) is more stable than I–(g) by 110 kJ mol–1.

B Cl–(g) is more stable than I–(g) by 37 kJ mol–1.
C I–(g) is more stable than Cl–(g) by 73 kJ mol–1.
D I–(g) is more stable than Cl–(g) by 183 kJ mol–1.

11 Internal combustion engines are most commonly used for mobile propulsion in vehicles and
portable machinery.

In mobile equipment like a car, the purpose of an internal combustion engine is to convert
chemical energy in fuel into kinetic energy so that the car can move. Currently, the easiest
way for the conversion is to burn the fuel inside the engine. This is advantageous since it can
provide high power–to–weight ratios together with excellent fuel energy density.

The following equation shows a reaction that takes place in an internal combustion engine.

2C8H18(g) + 25O2(g) → 16CO2(g) + 18H2O(g)

What are the signs for ∆H, ∆S and ∆G for this reaction?

∆H ∆S ∆G
A – + +
B – + –
C + – +
D + – –

AJC Prelim 2010 9647/01/H2 [Turn over

For each of the following questions, 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. The responses A to D
should be selected on the basis of:

A B C D
1, 2 and 3 1 and 2 only 2 and 3 only 1 only is
are correct are correct are correct correct

31 Which of the pairs contain a giant ionic compound and a simple molecular compound?

1 Al2O3 and Al2Cl6

2 SiO2 and SiCl4
3 P4O10 and PCl3

32 The compound sodium borohydride, NaBH4, is commonly used as a source of the hydride
anion for synthetic purposes.
Which types of bonding are found in the compound?

1 ionic
2 covalent
3 hydrogen bonding

33 Which equations represent the standard enthalpy change of reaction?

7
1 C2H6(g) + O2(g) Æ 2CO2(g) + 3H2O(l)
2
3 3
2 Fe(s) + O2(g) + H2(g) Æ Fe(OH)3(s)
2 2
3 3C(s) + 3H2(g) Æ CH2=CHCH3(g)

CJC H2 Preliminary Examination 2010 12

 4

8 Amyloids are insoluble fibrous protein aggregates sharing specific structural traits and are
linked to various neurodegenerative diseases. The folding of amyloids into specific shape
under physiological condition is a spontaneous process. What are the correct signs for ΔG,
ΔH and ΔS?

ΔG ΔH ΔS
A + + +
B – – –
C – + –
D – – +

9 When 13.08 g of zinc dust is added to 250 cm3 of 1.0 mol dm–3 aqueous copper(II) sulfate,
the temperature rises by 15 °C. The specific heat capacity of the final solution is
4.20 J g–1 K–1.
Cu2+ + Zn ⎯→ Zn2+ + Cu

What is the enthalpy change for the above reaction?

A –4.12 kJ mol–1 B –66.3 kJ mol–1 C –78.8 kJ mol–1 D –82.9 kJ mol–1

10 A mass of 1.66 g CuSO4.5H2O is dissolved and added to an excess of KI(aq).

2Cu2+(aq) + 4I–(aq) ⎯→ Cu2I2(s) + I2 (aq)

The iodine liberated is titrated against aqueous sodium thiosulfate, which is oxidised
according to the following equation.
2S2O32– ⎯→ S4O62– + 2e

What volume of 0.150 mol dm–3 Na2S2O3(aq) is required to react with the iodine liberated?

A 11 cm3 B 22 cm3 C 44 cm3 D 89 cm3

© DHS 2010 9647/01/Prelim 2010 [Turn over

 3

4 Use of the Data Booklet is relevant to this question.

The H−Cl bond energy is not the mean of the H−H and Cl−Cl bond energies.
Which of the following statements explain this observation?
A HCl is very stable to heat.
B HCl is completely dissociated into ions, but not H2 and Cl2.
C The H−Cl bond is very polar.
D The H−H bond is much stronger than the Cl−Cl bond.

5 When compared at the same pressure and temperature, which one of the
following properties has the same value for H2 and for D2? [D = 21H ]

A density
B average molecular speed
C rate of intermolecular collision
D average molecular kinetic energy

6 Given the following enthalpy change

N2(g) + 3H2(g) → 2NH3(g) ∆H• = –92 kJ mol−1
N2(g) + 4H2(g) + Cl2(g) → 2NH4Cl(s) ∆H• = –629 kJ mol−1
NH3(g) + HCl(g) → NH4Cl(s) ∆H• = –176 kJ mol−1
What is the standard enthalpy change of formation of gaseous hydrogen
chloride?
A – 46.3 kJ mol-1
B – 92.5 kJ mol-1
C – 180 kJ mol-1
D – 361 kJ mol-1

H2 Chemistry 9647/01 NYJC J2/10 PX [Turn over

 4

7 The enthalpy level diagram shown represents the dissolving of anhydrous

magnesium sulfate in a large volume of water.
Enthalpy

Mg2+(g) + 2SO42−(g)

∆H1
∆H2

MgSO4(s)

MgSO4 (aq)

Which statement is correct?

A The enthalpy change of solution of anhydrous magnesium sulfate is equal to
−∆H1 + ∆H2.
B The enthalpy change of solution of anhydrous magnesium sulfate is expected
to be less positive than that of barium sulfate.
C The solvation process is independent of temperature.
D Dissolving magnesium sulfate results in a decrease in the temperature of the
solution.

8 Photochromic glass, used for sunglasses, darkens when exposed to bright light
and becomes more transparent again when the light is less bright. The depth of
colour of the glass is related to the concentration of silver atoms.
The following reactions are involved.
reaction 1 Ag+ + Cl− → Ag + Cl
reaction 2 Cu+ + Cl Cu2+ + Cl−
reaction 3 Cu2+ + Ag → Cu+ + Ag+
Which statement about these reactions is correct?
A Cu+ and Cu2+ ions act as heterogeneous catalysts.
B Cu+ and Cu2+ ions act as homogeneous catalysts.
C Cu+ and Cu2+ ions act as autocatalysts.
D Light acts as a negative catalyst (inhibitor) in reaction 1.

H2 Chemistry 9647/01 NYJC J2/10 PX

 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 For which of the following pairs does the first species have a smaller bond angle?

1 OCl2, SnCl2
2 NF3, NCl3
3 I3–, N3–

32 Given only the standard enthalpy changes of combustion of carbon, hydrogen and
methane, which of the following can be calculated?

1 The enthalpy change for the hypothetical reaction:

2CO2(g) + 4H2O(l)  2CH4(g) + 4O2(g).
2 The enthalpy change of formation of water.
3 The enthalpy change of formation of liquid methane.

33 A 20 cm3 solution contains 1 x 10–3 mol dm–3 X+ and 1 x 10–3 mol dm–3 Y2+ metal ions.
7 x 10–4 mol of solid sodium sulfate is added to the solution. The numerical values of the
solubility product of X and Y sulfates are 7.4 x 10–7 and 9.1 x 10–6 respectively. What can
be deduced from this information?

1 The metal Y sulfate will precipitate out selectively.

2 There are more X+ ions than Y2+ ions remaining in the solution.
3 The solubility products of metal X and Y sulfates will change when 2 g of solid
sodium sulfate is added to the solution.

34 A sample of copper which contains silver and zinc impurities can be purified by
electrolysis. Which of the following statements are true?

1 The impure copper is made the anode.

2 Both zinc and silver are preferentially oxidised to its ions.
3 The concentration of the copper(II) ions in the electrolyte remains constant.

13
 2
(g) It is more appropriate to measure the mass of water formed as the difference in the
mass of H2O formed is larger.
[Total: 12]

2 (a)(i) Cr2O3 + 2OH– + 3H2O  2Cr(OH)4–

(a)(ii)  In the presence of ligands, the partially–filled 3d orbitals of Cr3+ are split into two
levels.
 The energy gap is small and corresponds to the visible light region.
 Energy is absorbed from the visible region when an electron promotes from a
lower energy d–orbital to a vacant higher energy d–orbital, i.e. d–d transition.
 Colour of Cr3+(aq) is complement to the colour absorbed.
 Al3+(aq) is colourless as the energy required for electronic transition from 2p to
3s is large and falls outside the visible light region.

(a)(iii) Cr3+ + 3e Cr Eo = –0.74 V

Mn2+ + 2e Mn Eo = –1.18 V
Al3+ + 3e Al Eo = –1.66 V

Mn can reduce Cr3+ as its Eo is more negative than –0.74V

Mn cannot reduce Al3+ as its Eo is less negative than –1.66V

(b) Hhyd of Cr3+ is less exothermic / smaller in magnitude than that of Al3+.

Cr3+ is larger / has a smaller charge density than Al3+,

thus forms weaker ion–dipole interaction with water molecules.

(c)(i)

Al3+(g) + 3Cl–(g)

Energy 577 + 1820 + 2740 + 3(–364)

= +4045

Al(g) + 3Cl(g)

3
/2(+244)
3
Al(g) + /2Cl2(g) –4690 + 3(–381)
= –5833
+326 3 x BE
Al(s) + 3/2Cl2(g)
0

–704
AlCl3(g)
AlCl3(s) +121

Hsoln
Al3+(aq) + 3Cl–(aq)

AJC/H2 Chemistry/JC2 Prelim2010

 3
By Hess’ Law,
Hsoln = –392 kJ mol–1

(c)(ii) By Hess’ Law,

bond energy of Al–Cl = +425 kJ mol–1
[Total: 15]

3 (a)(i) (10 pH )2

Ka1  = 4.3 x 10–7 mol dm–3
0.100
 pH = –lg (4.3 x 10–7 x 0.100)1/2 = 3.68

(a)(ii) H2CO3 + Ba(OH)2  BaCO3 + 2H2O

n(Ba(OH)2) = n(H2CO3)
0.0625 x V = 0.100 x 25

volume of Ba(OH)2 required = 40 cm3


(a)(iii) [HCO 3 ][H  ]
Ka1 =  pH = pKa1 = 6.37
[H 2 CO 3 ]

(a)(iv)
pH

6.37
3.68
Volume of Ba(OH)2/cm3
0 10 20 40

(b)(i) On addition of H+, HCO3– + H+  H2CO3

On addition of OH–, H2CO3 + OH–  HCO3– + H2O

(b)(ii) [HCO 3 ]
pH = pKa1 + lg
[H2 CO 3 ]
[HCO 3 ] [HCO 3 ]
lg = 7.4 – 6.37 = 1.03  = 10.7
[H2 CO 3 ] [H2 CO 3 ]

(b)(iii) [HCO 3 ]
= 10.7
[H2 CO 3 ]
 [HCO3–] = 10.7 x 2.4 x 10–2 = 0.257 mol dm–3

AJC/H2 Chemistry/JC2 Prelim2010

4(a) Phosphorus pentachloride is a greenish–yellow crystalline solid with an irritating odour. It is
corrosive to metals and tissue. Long–term exposure to low concentrations or short–term exposure
to high concentrations can result in adverse health effects. Phosphorus pentachloride can be
synthesised using the following reaction.

PCl3(s) + Cl2(g)  PCl5(s)

Given the following thermochemical data,

Hf (PCl3) = –315 kJ mol–1

Hf (PCl5) = –408 kJ mol–1

(i) calculate the standard enthalpy change of reaction for the synthesis of phosphorus
pentachloride; and

Hrxn = –408 – (–315) = –93 kJ mol–1

(ii) calculate the average P–Cl bond energy.

–93 = 3x + 244 – 5x
2x = 337
x = Bond energy of P–Cl = +168.5 = +169 kJ mol–1

(iii) Assuming that enthalpy change of reaction does not change with temperature, predict if the
synthesis of phosphorus pentachloride is more feasible at 298K or 333K.

There is a decrease in number of moles of gaseous species resulting in more negative

entropy. The synthesis is less feasible at 60C since higher temperature will result in a
less negative Gibbs’ free energy.

(iv) The volume of chlorine gas used for the synthesis at 25 C is 17.5 dm3. Calculate the
volume of chlorine for the synthesis at 60 C.

V60
333
× 17.5 = × 17.5
V25 298
Volume at 60 C = 19.6 dm3 (3 sig fig)

(v) A student attempts to carry out the synthesis in a laboratory. State one precaution that the
student should take.

Either one:
 Perform reaction in a fumehood / fume cupboard as chlorine is an irritant gas.

 Wear protective equipment such as gloves and eye goggles as phosphorous

pentachloride is corrosive.
[5]

(b) Chlorine is found primarily as the chloride ion, a component of the salt that is deposited in
the earth or dissolved in the oceans – about 1.9% of the mass of seawater is chloride ions. Even
higher concentrations of chloride are found in the Dead Sea and in underground brine deposits.

© DHS 2010 9647/02/Prelim 2010 7

(i) Using the following data and relevant data from Data Booklet, construct a
Born–Haber cycle for magnesium chloride.

Hf (MgCl2) = –641 kJ mol–1

Hat (Mg) = +150 kJ mol–1
First electron affinity of chlorine = –349 kJ mol–1

–1
energy/ kJ mol

Mg2+(g) + 2e + 2Cl(g)

2nd IE (Mg) 2 x 1st EA(Cl)

Mg+(g) + e + 2Cl(g)
st
Mg2+(g) + 2Cl–(g)
1 IE (Mg)
Mg(g) + 2Cl(g)

BE (Cl2) Hlatt
Mg(g) + Cl2(g)

Hat(Mg)
Mg(s) + Cl2(g)
0
Hf(MgCl2)
MgCl2(s)

(ii) Hence, calculate the lattice energy for magnesium chloride.

Hlatt = –641 – [150 + 244 + 736 + 1450 – 2(349)] = –2520 kJ mol–1 (3sf)
[4]

(c) At 373K, both phosphorus trichloride and nitrogen trichloride exist as a gas.

(i) State one assumption of ideality in a gas.

Any 1 assumption:

The molecules of a gas are in constant random motion, moving in straight lines unless
they collide with the walls of the container or with another molecule.

The molecules have negligible volume i.e. the volume of the molecules is negligible
compared with that of the container.

The collisions which occur between these molecules are perfectly elastic.

The forces of attraction between the molecules (intermolecular attraction) as well as

between the molecules and walls of the container are negligible.

© DHS 2010 9647/02/Prelim 2010 8

 HCl(g) → H+(g) + Cl−(g)

Enthalpy change of formation of HCl(g) = −92 kJ mol−1

Electron affinity of Cl(g) = −364 kJ mol−1 [4]

H«(g) + Cl–(g)
Energy

1st IE (H) + 1st EA

H(g) + Cl(g)
ΔHrxn
½ BE(H−H) + ½ BE(Cl−Cl)

½H2(g) + ½Cl2(g)
0
ΔHf (HCl)
HCl (g)

ΔHrxn = − ΔHf (HCl) + ½ BE(H−H) + ½ BE(Cl−Cl) + 1st IE (H) + 1st EA

ΔHrxn = −(−92) + ½(436) + ½(244) + 1310 + (−364)
ΔHrxn = + 1378 kJ mol−1

(ii) Explain the difference between your answer from (c)(i) with the standard
enthalpy change for the process shown below.
HCl(g) + aq → H+(aq) + Cl−(aq) ΔH = −75 kJ mol−1 [2]

[Total: 20]

Reaction 2 involves forming ion-dipole interactions between H+ and water

molecules and Cl− and water molecules. Energy is evolved in the formation
of ion-dipole interactions which can more than compensate the heat
absorbed to break the H−Cl bond in the gaseous state and to ionise the H
atom, thus resulting in the enthalpy change of reaction 2 to be exothermic.

H2 Chemistry 9647/03 NYJC J2/10 PX [End of Paper]

 3

(ii) O O

N CH C + [O] N CH C + H2O
H CH2 H CH2

SH S
+
S
SH
CH2 O
CH2 O
N CH C
N CH C
H
H

(iii) Ionic interactions, hydrogen bonding and van der Waals’ forces.

(iv) Heavy metal ions form ionic interactions with the −COO− groups on the
side chains and disrupt the ionic interactions in the tertiary structure.
This brings about the formation of insoluble protein salts (i.e.
precipitation of protein) and leads to denaturation.
Heavy metal ions have a high affinity for sulfur and disrupt the disulfide
bridges in the tertiary structure, leading to denaturation.

(c) (i) The standard enthalpy change of combustion of mercaptopurine is the

energy change when one mole of mercaptopurine is completely burnt in
oxygen under standard conditions of 298 K and 1 atm.
C5H4N4S(s) + 7O2(g) → 5CO2(g) + SO2(g) + 2N2(g) + 2H2O(l)
(state symbols required)

(ii) Δ Hc = [2E(N—H) + 2E(C—H) + 2E(C=N) + 6E(C—N) + E(C=C) +

E(C=S) + E(C—C) + 7E(O=O)] – [10E(C=O) + 2E(S=O) +
2E(N≡N) + 4E(O—H)]
= [2(+390) + 2(+410) + 6(+305) + 2(+610) + (+610) + (+138)
+(+350) + 7(+496)] – [10(+740) + 2(+128) + 2(+994) + 4(+460)]
= +9220 – (+11484)
= –2264 kJ mol−1

(iii) Heat absorbed by water = 100 × 4.18 × (87 – 25)

= 2.59 × 104 J
100
Heat evolved by combustion = × 2.59 × 104
65
= 3.98 × 104 J
1.50
Amount of mercaptopurine =
5 × 12.0 + 4 × 1.0 + 4 × 14.0 + 32.1
= 0.00986 mol

River Valley High School 9647/03ANS/PRELIM/10

Preliminary Examination 2010
 4

3.98 × 104
ΔHc = −
0.00986
= −4.04 × 106 J mol−1
= −4040 kJ mol−1

(iv) The value for ΔHc obtained from bond energies in (c)(ii) is not accurate
as the bond energies quoted from the Data Booklet represent average
bond energies derived from the full range of molecules that contain the
particular bonds.
Mercaptopurine and H2O are in the solid and liquid states respectively
under standard conditions but the calculation in (c)(ii) makes use of
bond energies which relate to breaking of covalent bonds in gaseous
molecules. The enthalpy change of sublimation of mercaptopurine and
enthalpy change of vapourisation of H2O are not accounted for in the
calculation of ΔHc.

3 (a) X− → X + e−

(b) (i) The reaction is autocatalytic as the Ag produced catalyses the reaction.
The rate of reaction increases at first due to the formation of the Ag
autocatalyst, then decreases as the reactants are used up.

(ii) Z undergoes condensation with 2,4-DNPH ⇒ Z is a carbonyl compound

/ contains ketone or aldehyde functional group
1 molar equivalent of Z undergoes electrophilic addition with 2 molar
equivalents of Br2 ⇒ Z contains two alkene functional groups
Z undergoes oxidation with hot acidified KMnO4(aq) to give two identical
compounds ⇒ Z contains a plane of symmetry
Y is insoluble in water (due to large hydrophobic benzene ring) but can
undergo acid-base reaction with NaOH(aq) ⇒ Y contains phenol or
carboxylic acid group
Y does not undergo acid-carbonate reaction with Na2CO3 ⇒ Y is not a
carboxylic acid, so Y contains phenol group
Y undergoes acid-metal reaction with Na ⇒ Y contains phenol group

HO OH O O

Y Z

(c) (i) ⎛ 1.0 ⎞

[CH3COO− ] ⎜ ⎟
pH = pKa + lg = −lg (1.8 × 10−5) + lg ⎜ 2 ⎟
[CH3 COOH] ⎜⎜ 1.0 ⎟⎟
⎝ 2 ⎠
= 4.74

River Valley High School 9647/03ANS/PRELIM/10

Preliminary Examination 2010