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2018 Y6 H2 Chemistry Preliminary Exams Paper 3 (Suggested Solutions)

Section A
1 (a) (i)

(ii) Since OH– is a catalyst, [OH–] is constant during each experiment and does not
affect the reaction rate.

Using Experiment I,
First t½ = 4.7 min. Second t½ = 9.5 – 4.7 = 4.8 min.

Since both t½ are approximately the same, the reaction is first order w.r.t. ethanal.

(iii) By drawing tangents at t = 0 min,

1.20 - 0
For Experiment I, initial rate = = 0.176 mol dm–3 min–1
0 - 6.8
1.20 - 0
For Experiment II, initial rate = = 0.353 mol dm–3 min–1
0 - 3.4

When [OH–] doubles, rate doubles. Hence, reaction is first order w.r.t. OH–.

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(iv) rate = k[OH–][ethanal]

(v) Initial rate method

Using Experiment I, 0.1765 = k(1.0)(1.2)  k = 0.147 mol–1 dm3 min–1

OR

Half-life method
ln 2
t½ =
k [OH- ]
ln 2
Using Experiment I, 4.75 =  k = 0.146 mol–1 dm3 min–1
k (1.0)

(b) (i) Mechanism: SN2 (or bimolecular nucleophilic substitution)

Let RCH2− represent A.

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(ii) total no. of particles with

number of particles
with a given energy energy Ea at temperature T1
T2 > T1
T1 total no. of particles with
T2 energy Ea at temperature T2

0 kinetic energy
Ea

An increase in temperature from T1 to T2 increases the average kinetic energy of the

reactant particles. More reactant particles have energy greater than or equal to the
activation energy of the reaction.

This results in an increase in effective collision frequency and hence an increase in

the rate of the reaction.

(iii) The C–Cl bond (BE = 340 kJ mol–1) is stronger than the C–Br bond (BE = 280 kJ
mol–1). Hence it is more difficult to break the C–Cl bond, resulting in a slower
reaction for 2-chlorobutane.

(iv) Hydroxide ions are less bulky and will experience less steric hindrance when
attacking the electron deficient carbon atom.
OR
In A, the negative charge is delocalised into the adjacent C=O group. Hence, lone
pair on A is less available, resulting in a slower reaction.

(c) (i)

(ii) Step 1: I2(aq) with NaOH(aq), heat or warm

Step 2: (catalytic) conc H2SO4, heat

2 (a) (i) PbF2, PbCl2 and PbBr2 have giant ionic structure with strong ionic bonds.

PbF2, PbCl2 and PbBr2 have the same cation and the anions have the same charge.
Since the ionic radius increases from F– to Br–, the interionic distance increases from
PbF2 to PbBr2. Hence the strength of ionic bond and melting point decreases from
PbF2 to PbBr2.
q+ q−
Or since |LE| ∝ and the ionic radius increases from F– to Br–, the LE
r+ + r−
become less exothermic, less energy is required to overcome the ionic bond and
melting point decreases from PbF2 to PbBr2.

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(ii) Due to its high charge and small size, Pb4+ has a high charge density and high
polarising power, which causes it to distort the electron cloud of Cl– to such an
extent that PbCl4 is predominantly a covalent compound.

Hence, PbCl4, having a simple covalent/molecular structure, consists of discrete

molecules held together by weak instantaneous dipole-induced dipole interactions
which requires a small amount of energy to overcome. Thus, it has a low melting
point.

(iii) 3.58 × 10-5

[I –] = 25.0 = 1.432 x 10–3 mol dm–3
1000
9.80 ×10-9
[Pb2+] in filtrate = 2 = 4.779 x 10–3 mol dm–3
(1.431 ×10-3 )
[Cl–] from PbCl2 in filtrate = 4.779 x 10–3 x 2 = 9.558 x 10–3 mol dm–3
Total [Cl–] in filtrate = 9.558 x 10–3 + 0.050 = 0.05956 mol dm–3
Ksp = [Pb2+][Cl–]2 = (4.779 x 10–3 )(0.05956)2 = 1.70 x 10–5 mol3 dm–9

(iv) H Pb Cl
mass 0.6 59.0 40.4
mole 0.6/1.0 59.0/207 40.4/35.5
= 0.6 = 0.285 = 1.138
≈2 ≈1 ≈4

Empirical formula = H2PbCl4

Actual formula = H2PbCl4
Complex ion = [PbCl4]2−

(v) The following equilibrium is established in the saturated solution:

PbCl2(s) ⇌ Pb2+(aq) + 2Cl−(aq) -----(1)

When concentrated hydrochloric acid is added and the mixture shaken, [Cl–] is
greatly increased. Pb2+ ions react with Cl− to form the soluble complex, [PbCl4]2−, as
shown below.
Pb2+(aq) + 4Cl−(aq) ⇌ [PbCl4]2−(aq) -----(2)

The formation of [PbCl4 ]2− decreases the [Pb2+] in the solution.

To counteract the decrease in [Pb2+], the equilibrium position of reaction (1) shifts to
the right i.e. PbCl2 dissolves.
or

[Pb2+] decreases due to the formation of [PbCl4 ]2−. When ionic product, [Pb2+][Cl−]2
becomes less than the Ksp , all the PbCl2 dissolves.

(b) (i) 2HI(g) ⇌ H2(g) + I2(g)

(ii) The thermal stabilities of HCl to HI, which is related to the H-X bond strength,

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increase in the order: HI < HBr < HCl

The stronger the H-X bond, the more thermally stable HX is. Since the bond strength
of HI < HBr < HCl, the thermal stability of HI < HBr < HCl.

The energy supplied by the red hot wire was insufficient to decompose HCl, hence
there is no observable change; was able to decompose some HBr, resulting in
reddish-brown vapour of Br2 formed slowly; and was able to decompose HI readily
to result in purple fumes of I2 evolved vigorously.

(c)

Square planar, 90˚

(d) Cl2 + 2e– ⇌ 2Cl– E = +1.36 V

Mn2+ + 2e– ⇌ Mn E = –1.18 V
MnO2 + 4H+ + 2e– ⇌ Mn2+ + 2H2O E = +1.23 V
MnO4– + 4H+ + 3e– ⇌ MnO2 + 2H2O E = +1.67 V

Considering the reaction between Cl2 and Mn, Ecell = +1.36 – (–1.18)
= +2.54 V (spontaneous)
Considering the reaction between Cl2 and Mn , E cell = +1.36 – 1.23
2+ 

= +0.13 V (spontaneous)

Considering the reaction between Cl2 and MnO2, Ecell = +1.36 – 1.67
= –0.31 V (not spontaneous)

Thus, Cl2 will oxidise Mn to Mn2+ and further oxidise Mn2+ to MnO2. (proven)

Overall eqn: 2Cl2 + Mn + 2H2O ⎯→ 4Cl– + MnO2 + 4H+

(e) PCl5(s) + 4H2O(l) ⎯→ H3PO4(aq) + 5HCl(aq)

3 (a) 1s22s22p63s23p63d54s1

(b) (i) Step I: acid-base (or complexation or complex formation)

Step II: oxidation / redox reaction
F: [Cr(OH)6]3–(aq) or [Cr(OH)4]–(aq)
G: Cr2O72−(aq)

(ii) The ability to display variable oxidation states in their compounds. This is due to the

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close similarity in energy between the 3d and 4s electrons, which thus allows for
different number of these electrons to participate in chemical bonding.
OR Ability to form complexes due to availability of low lying vacant orbitals.

(c) (i)
z z

(ii) In an octahedral environment, lone pairs on the ligands approach the central metal
ion along the x, y and z axes.

3dx2-y2 and 3dz2 orbitals have their greatest electron density along the co-ordinate
axes on which the ligands are situated. Hence electrons in these orbitals are pointing
towards the lone pairs of ligands, and will be repelled by them.

3dxy, 3dyz, 3dxz orbitals have their greatest electron density in between the
co-ordinate axes. Hence the repulsion between electrons in these orbitals and those
of the approaching ligands will be less compared to electrons in 3dx2-y2 or 3dz2
orbitals.

Hence the d-orbitals are split into two different energy levels.

(d) (i) [Cr(H2O)4Cl2]+

[Cr(H2O)5Cl]2+
[Cr(H2O)6]3+

(ii) The presence of ligands causes the splitting of the five 3d orbitals in Cr3+ into two
sets of slightly different energy levels. Since the 3d subshell in Cr3+ are partially
filled, electrons from the lower-energy d orbitals can absorb energy and get
promoted to the higher-energy d orbitals (d-d transition). The energy absorbed
corresponds to certain wavelength from the visible light spectrum and the colour
observed is the complement of the colour absorbed.

(iii) Chloride and water are ligands of different strength. Different proportions of these
ligands cause the d orbitals to be split to different extents, creating different energy
gaps for different complexes, which in turn absorb energies of different wavelengths
from the visible light spectrum, thus displaying different colours.

(iv)

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(e) (i) Positive (∆S > 0). There is increase in disorder/entropy due to increase in number of
particles / molecules / species formed.

(ii) ∆H value of the forward reaction is close to zero as the type (N→Cr coordinate
bond) and the number of dative covalent bonds broken and formed are about the
same.

(iii) ∆G = ∆H – T∆S
Since ∆H is close to zero and ∆S is positive, ∆G (for the forward reaction) will be
more negative at a higher temperature, hence increasing the yield of complex H.

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Section B

4 (a) (i) Na2O reacts with water to form a strongly alkaline solution (pH ≈ 13 – 14).
Na2O(s) + H2O(l) ⎯→ 2NaOH(aq)

SiO2 does not dissolve in water because of the strong Si–O covalent bonds in the
giant molecular structure. Solution remains neutral (pH = 7).

P4O10 reacts with water to form an acidic solution (pH ≈ 2).

P4O10(s) + 6H2O(l) ⎯→ 4H3PO4(aq)
(Note: H3PO4 is a weak acid)

(ii) (MgO is an ionic oxide which is basic and react with acids. SO3 is a covalent oxide
which is acidic and reacts with bases.)

Al2O3 (an amphoteric oxide) reacts with both acids and bases as it is an ionic oxide
with covalent character. The covalent character is due to the high charge
density/polarising power of Al3+ that polarise and distort the electron cloud of O2−.

With acid: Al2O3(s) + 6H+(aq) → 2Al3+(aq) + 3H2O(l)

With base: Al2O3(s) + 2OH−(aq) + 3H2O(l) → 2[Al(OH)4]−(aq)

(b) (i) Step 1: nucleophilic addition

(ii) In primary amides, the lone pair of electrons on the nitrogen atom interacts with the
π electron cloud of the adjacent C=O bond and is delocalised. Hence, the lone pair
of electrons is not available for donation to the electrophilic carbonyl carbon atom
/unable to act as a nucleophile in step 1.

(iii)

(c) (i) Step 1: NaOH(aq), heat

Step 2: (anhydrous, rtp)

Step 3: excess CH3Cl, heat

(ii)

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(iii) Possible structures for S (C6H12BrN):

Possible structures for T (C6H12BrN):

S and T are constitutional / structural / positional isomers.

(iv) In T, the p orbital of Br overlaps with the π electron cloud of the adjacent C=C bond
and the lone pair of electrons in the p orbital of Br delocalises into the C=C bond and
results in partial double bond character in the C–Br bond.

Hence, T does not undergo nucleophilic substitution and no Br− are present to react
with Ag+ to form pale cream ppt of AgBr.

(S is an alkyl bromide that can undergo nucleophilic substitution when heated with
ethanolic AgNO3 to form alcohol and Br−. Br− then forms the pale cream ppt of AgBr
with Ag+.)

5 (a) Constitutional / Structural / Functional group isomerism

(b)

(c) (i) Enantiomerism

CH2CH3 CH2CH3
C6H5 NH C6H5 NH

O N O O N O
CH3 CH3

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(ii) Test: To separate samples of X and phenytoin, add NaOH(aq) and heat strongly.

Observation: Pungent gas (NH3) that turns moist red litmus blue is evolved for the
sample containing phenytoin but no pungent gas is evolved for the sample
containing X.

(d) (i) Mr (J) = 190

n(J) = 5/190 = 0.02632 mol; n(H2) = 2(0.02632) = 0.05264 mol

pVH2 = nRT
(1.0 x 105) VH2 = (0.05264)(8.31)(273 + 150)
VH2 = 1.85 x 10–3 m3 = 1.85 dm3

(ii) Information / Reaction Deduction / Explanation

J has molecular formula, J is likely to contain a benzene ring due
C10H10N2O2 to the relatively high C to H ratio.
J exhibits optical activity J contains a chiral centre and/or no
plane of symmetry.
J is neutral. J contains amide and/or –CN group. Or
J is not carboxylic acid or amine or
phenol.
J has no reaction with 2,4-DNPH J is not aldehyde & ketone / carbonyl
Reduction of nitrile.
H2(g) / Ni
J ⎯⎯⎯⎯⎯⎯→o
150 C K Since C=C is absent and there is
increase of 4 H atoms from J to K, J
contains –CN group.
J contains amide/ester/nitrile and
H2SO4(aq) undergoes acidic hydrolysis.
J ⎯⎯⎯⎯→ CO2 + resultant mixture
heat
distillation

residue + distillate L

base Residue is an ionic salt. (M is a base.)

residue ⎯⎯→ M

M undergoes electrophilic substitution.

Br2(aq)
M ⎯⎯→ N (C6H4NBr3)

N is

Hence M is

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hot alkaline I2(aq)

L ⎯⎯⎯⎯⎯⎯⎯→ yellow ppt

L contains the group

L decolourises acidified L undergoes oxidation to form P. Hence,

KMnO4(aq) to form P P is a methyl ketone / carbonyl
compound.
(L cannot be a methyl ketone since J is
not carbonyl compound and L is
oxidised by KMnO4 to form P.)

2,4-DNPH
P ⎯⎯⎯⎯⎯→ Q (orange ppt)
Hence, L (C3H6O3) is

P is

Condensation

Q is
Combining the above deductions,
J can be:

K can be:

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