You are on page 1of 11

Advo Education Group Pte Ltd

Practice Paper 7

Reg. No. 200710217Z

Suggested Solution Practice Paper 11


Organic chemistry and ionic eqm Adapted from 2014 AJC P3 Q3
(a)

(i)

Since Ka1 >>> Ka2, only the first dissociation makes an appreciable contribution to the
pH of the solution. Thus, the H+ from Ka2 is ignored.
K a1

[HA - ][H3O ]
[H3O ] 2

[H2A]
[H2A]i

1.30 x 102

[H3O ]2
0.10

[H3O+] = 0.03606 mol dm3


pH = log[H3O+] = 1.44
(ii)

A2 + 2Na+ + 2H2O

2NaOH + H2A

No. of moles of A2 formed = (25/1000) x 0.10 = 0.0025 mol


No. of moles of NaOH required for complete neutralisation
= 0.0025 x 2 = 0.00500 mol
Volume of NaOH required = (0.0050 / 0.10) x 1000 = 50 cm3
[A2] =
(iii)

0.0025
1000 0.0333 mol dm3
25 50

A2 + H2O
K b1

HA + OH

[HA ][OH ] [OH ] 2

[A 2- ]
[A 2- ]i

Kb1 = Kw / Ka2
= 1014 / (5.90 x 107) = 1.695 x 108 mol dm3
1.695 x 108

[OH ]2
0.03333

(allow ecf marking)

[OH] = 2.377 x 105 mol dm3


pOH = log[OH] = 4.62
pH = 14 4.62 = 9.38

Page11

A is Easy with ADVO!


Tel: (65) 6251 3359 / 8233 2753 www.advoedu.com 1 Goldhill Plaza #02-43 Singapore 308899

Advo Education Group Pte Ltd

Practice Paper 7

Reg. No. 200710217Z

(a)

(iv)

pH
12.0
9.38
6.23

1.89
1.44
12.5 25.0

37.5 50.0 60.0

volume of NaOH / cm3

[1m] for correct shape of curve until 50 cm3.


[1m] for correct indication of 2 equivalence points at 25.0 cm 3 and 50.0 cm3 with
corresponding pH at 9.38.
[1m] for correct indication of 2 pK a values (1.89 and 6.23) and corresponding volumes
(12.5 cm3 and 37.5 cm3)
(v)

Indicator: thymolphthalein
The working pH range of thymolphthalein lies within the range of rapid pH change at the
end point.
or
The pH at the second equivalence point is within the working pH range of
thymolphthalein.

(b)

(i)

O
H

C
C

C
H

H
O

O
trans

cis

[1m] for correct displayed formulae


[1m] for correct labelling

Page11

A is Easy with ADVO!


Tel: (65) 6251 3359 / 8233 2753 www.advoedu.com 1 Goldhill Plaza #02-43 Singapore 308899

Advo Education Group Pte Ltd

Practice Paper 7

Reg. No. 200710217Z

(b)

(ii)

There is intramolecular hydrogen bonding involving H of OH group with the


neighbouring C=O group. Hence, there are fewer sites available for intermolecular
hydrogen bonds to be formed between the molecules. Less energy is needed to
overcome the less extensive intermolecular Hbonding during melting.
or
Cisbutenedioic acid results in kinks which cause the molecules to be less closely
packed in the structure. Less energy is required to overcome the intermolecular forces.

(c)

(d)

CH3
C

CH3
CH2CH2

CH3

CH2

OH

accept

HO

CH2

CH3
CH2CH2

geraniol

CH3
CH3

or

HO

CH2CH2CH2

CH3 H

CH3
CH3

O
N
CH3
P
Q
R

CH3

O
HO

O
CH2CH2

O
-

C
C

CH3

O
CH2CH2

O
HO

C
C

O-

O
CH2CH2

OH

A is Easy with ADVO!


Tel: (65) 6251 3359 / 8233 2753 www.advoedu.com 1 Goldhill Plaza #02-43 Singapore 308899

Page11

Practice Paper 7

Advo Education Group Pte Ltd


Reg. No. 200710217Z

[1m] each
Reaction
1. 1 mole of geraniol
decolourises 2 moles
of Br2(aq)

Type of reaction
electrophilic addition

2. Heating geraniol with

oxidative cleavage

excess conc. acidified


KMnO4(aq) produces
N, P and a colourless
gas.
3. Both N and P react
with 2,4
dinitrophenylhydrazine

4. P gives a yellow
precipitate and
compound Q on
warming with alkaline
aqueous iodine
5. R can be produced
from butenedioic acid
on reaction with H2 in
the presence of a
catalyst

condensation

Deduction
Presence of two C=C
bonds in geraniol
Presence of more than
one C=C bond in geraniol
The colourless gas is
CO2.
Presence of ketone group
in N and P

triiodomethane reaction
or oxidation

Presence of CH3CO
group in P

reduction / hydrogenation

R is
O
HO

O
CH2CH2

OH

Page11

[2m] for any correct 3 out of the 5 points


[1m] for any correct 2 out of the 5 points

A is Easy with ADVO!


Tel: (65) 6251 3359 / 8233 2753 www.advoedu.com 1 Goldhill Plaza #02-43 Singapore 308899

Advo Education Group Pte Ltd

Practice Paper 7

Reg. No. 200710217Z

Reaction Kinetics Adapted from 2014 PJC P3 Q1d


The kinetics of the uncatalysed reaction between peroxodisulfate ions and iodide ions can be
investigated experimentally.
S2O82(aq) + 2I(aq) 2SO42(aq) + I2(aq)
To find the rate equation: rate = k[S 2O82(aq)]a[I(aq)]b for this reaction, a continuous method with
sampling is used.
In an experiment, 50.0 cm3 of 0.200 mol dm3 of aqueous sodium iodide was mixed with 50.0 cm 3 of
2.00 mol dm3 aqueous sodium peroxodisulfate. At various time intervals, 10.0 cm3 of the reaction
mixture was withdrawn and quenched with 50 cm3 of ice-cold water. The resultant mixture was
titrated against 0.0250 mol dm3 aqueous potassium thiosulfate, K2S2O3, using starch as an
indicator.
The reaction between thiosulfate and iodine is as follows:
2S2O32 + I2 S4O62 + 2I
The results are shown below:
Time / min
Volume of K2S2O3 (aq) / cm3
(a)

0
0

2
9.50

4
17.00

6
22.50

12
32.25

16
35.50

Show that 40.00 cm3 of aqueous potassium thiosulfate is required to react with 10.0 cm 3 of
the reaction mixture when the reaction between peroxodisulfate and iodide ions is
complete.
n(I) = (50.0/1000)(0.200) = 0.010 mol (limiting reagent)
n(S2O82) = (50.0/1000)(2.00) = 0.10 mol
n(I2) produced in 100 cm3 of reaction mixture = 0.010 / 2
= 0.00500 mol
n(I2) in 10.0 cm3 = 0.00500 / (100/10.0)
= 0.000500 mol
n(S2O32) = 0.000500 x 2
= 0.00100 mol
volume of S2O32 needed = 0.00100 / 0.0250
= 0.040 dm3
= 40.00 cm3 (shown)

Page11

A is Easy with ADVO!


Tel: (65) 6251 3359 / 8233 2753 www.advoedu.com 1 Goldhill Plaza #02-43 Singapore 308899

Practice Paper 7

Advo Education Group Pte Ltd


Reg. No. 200710217Z

(b)

By drawing a suitable graph, use it to show that the reaction is first order with respect to I-.

(c)

The order of reaction with respect to S 2O82 is reported to be one. You are required to
conduct a second experiment using the same experimental procedures to confirm the order
of reaction.
Suggest suitable concentrations of aqueous sodium iodide and sodium peroxodisulfate to
be used and explain how the data obtained could be used to confirm the order of reaction.
Mix 50.0 cm3 of 0.200 mol dm-3 of aqueous sodium iodide with 50.0 cm3 of 4.00 mol dm3 (or
any other appropriate concentration) aqueous sodium peroxodisulfate and plot a volume
of S2O32 needed against time, the gradient of the graph at time = 0 should be doubled
compared to the first experiment if it is first order wrt S2O82 OR t1/2 is half.
Or
Mix 50.0 cm3 of 0.200 mol dm3 of aqueous sodium peroxodisulfate with 50.0 cm3 of
2.00 mol dm3 aqueous sodium iodide and plot a volume of S2O32 needed against time, the
half life should be constant if it is first order wrt S 2O82-. Note that in this case, I is added in
excess.
[Total: 7]

Page11

A is Easy with ADVO!


Tel: (65) 6251 3359 / 8233 2753 www.advoedu.com 1 Goldhill Plaza #02-43 Singapore 308899

Practice Paper 7

Advo Education Group Pte Ltd


Reg. No. 200710217Z

Electrochemistry Adapted from 2011 AJC/P3/5


(a)

(i)

In the presence of water ligands, the partially filled 3d orbitals in vanadium ions are
split into two levels (nondegenerate) with a small energy gap (correspond to
visible light region)
Energy is absorbed from the visible region when an electron promotes from a
lower energy level d orbital to a vacant higher energy level d orbital, i.e. dd
transition.
The colour observed is the complement of the colour absorbed.

(ii)

2VO3 + 8H+ + Zn
Zn2+ + 2VO2+ + 4H2O
o
E cell = 1.00 ( 0.76) = +1.76 V > 0
2VO2+ + 4H+ + Zn
Zn2+ + 2V3+ + 2H2O
o
E cell = 0.34 ( 0.76) = +1.10 V >0
2V3+ + Zn
2V2+ + Zn2+
o
E cell = 0.26 ( 0.76) = +0.50 V >0
Eocell = 1.20 ( 0.76) = 0.44 V <0
From the Eocell calculations, VO3 will be reduced by Zn to V 2+, and the final colour of
the solution will be violet.

(iii)

n(NH4VO3) reacted =

3.00
= 0.0257 mol
(14 + 4 + 50.9 + 16 3)

n(SO2) = (0.0257)
= 0.01285 mol
Volume of SO2 needed = 0.01285 x 24000
= 308 cm3
(b)

(i)

A homogeneous catalyst is a catalyst that is in the same phase as the reactants.

(ii)

Step 1: Formation of intermediate


2VO2+ + 4H+ + 2I
2VO2+ + 2H2O + I2
Eocell = 1.00 0.54 = +0.46 V > 0
Step 2: Regeneration of the catalyst
2VO2+ + 2H2O + S2O82
2VO2+ + 4H++ 2SO42
Eocell = 2.01 1.00 = +1.01 V > 0

(c)

(i)

cathode: VO2+ + 2H+ + e


anode: V2+
V3+ + e

(ii)

Eocell = 1.00 (0.26)


= +1.26 V

VO2+ + H2O

(iii) This helps to maintains electrical neutrality (prevent build up of charges in the two
A is Easy with ADVO!
Tel: (65) 6251 3359 / 8233 2753 www.advoedu.com 1 Goldhill Plaza #02-43 Singapore 308899

Page11

Advo Education Group Pte Ltd

Practice Paper 7

Reg. No. 200710217Z

half cells) so that electrical energy can continue to flow.


(d)

Q = It = 14 x 20 x 3600 = 1.008 x 106 C


n(VO2+) = n(e) = 1.008 x 106/96500 = 10.45 mol
[VO2+] initially = 10.45/5
= 2.09 mol dm3

(e)

(i)

Any Eo value that is more negative than that of EoV3+/V2+ = 0.26V


and its corresponding Eocell value correctly calculated.

(ii)

Larger minimum external e.m.f needed to recharge the cell.


[Total: 20]

Electrochemistry Adapted from 2011 ACJC/P3/4


4

A chemist design an ion-specific probe for measuring [Ag +] in a NaCl solution saturated with
AgCl using the following set- up.
voltmeter

Pt wire

Ag wire

Paste of Hg2Cl2 in
Hg

Salt Bridge

Saturated KCl
solution
NaCl solution
saturated with AgCl
(i)

Given the following standard half reactions.


Hg2Cl2(s) +2e
Ag+(aq) + e

2Hg(s) + 2Cl-(aq)

Ered = +0.24 V

Ag(s)

Ered = +0.80 V

Obtain an overall balanced equation, including state symbols for the cell above
and state the direction of the flow of electron in the cell.
[2]
2Ag+(aq) + 2Cl(aq) + 2 Hg(s) Hg2Cl2(s) + 2Ag(s) [1]
From Pt to Ag
[1]
A is Easy with ADVO!
Tel: (65) 6251 3359 / 8233 2753 www.advoedu.com 1 Goldhill Plaza #02-43 Singapore 308899

Page11

(a)

Advo Education Group Pte Ltd

Practice Paper 7

Reg. No. 200710217Z

(a)

(ii)

An engineer wish to use the probe to analyse an ore sample. After pretreating the
sample, the chemist measured the cell voltage, Ecell as 0.53V.
The Nernst equation can be used to measure the concentration of silver ions using
the probe,

Ecell = Ecell

0.0592
log10 K
n

Where n is the no of moles of electrons transferred in the overall reaction and K is


the equilibrium constant for the overall equation in a(i).
Assuming the concentration of Cl is so high that it is essentially constant, use
the Nernst equation to calculate the concentration of silver ions in the ore sample [3]
K = 1/ [Ag+]2 since [Cl-] is high and effectively constant) [1]
n=2
[1]
0.0592
0.53 = 0.56
log10 1/ [Ag+]2
n
[Ag+] = 0.311 mol dm3 [1]
(iii)

Given that,
AgCl(s) + e

Ag(s) + Cl(aq) Ered = +0.22 V

Using the half equation above and any other relevant data from the Data Booklet,
derive the Ecell for the overall reaction: Ag+(aq) + Cl(aq)
AgCl(s) and use
the equation given in a(ii), calculate a value of the Ksp for silver chloride at
equilibrium, if Ecell of any process at equilibrium is 0V.
[3]
Ag+(aq) + Cl(aq)

AgCl(s)

Ecell = +0.80 0.22 = 0.58V

[1]

Given that for a process at equilibrium, the Ecell = 0V


K = 1 / Ksp(AgCl) and n = 1
[1]
0.0592
0 = 0.58
log10 1/Ksp
n
1/Ksp = 6.27 x 109
Ksp = 1.59 x1010 mol2dm6

[1]

Page11

A is Easy with ADVO!


Tel: (65) 6251 3359 / 8233 2753 www.advoedu.com 1 Goldhill Plaza #02-43 Singapore 308899

Practice Paper 7

Advo Education Group Pte Ltd


Reg. No. 200710217Z

(b)

(i)

To prepare the saturated solution of AgCl and NaCl. AgCl is added to a 200 cm3
solution of NaCl of concentration of 1 x 103 mol dm-3. Using the Ksp value obtained
in a(iii), predict the maximum mass of AgCl to be added to obtain a saturated
solution. If you had not been able to obtain a value for the Ksp in a(iii), assume a
value of 1.59 x 1010 mol2 dm6
[2]
Ksp = [Ag+][Cl] = 1.59 x 1010
Let s be the solubility of AgCl in the given NaCl solution.
(s )(s+ 1 x 10-3) = 1.59 x 1010
Assume s << 1.0 x 103,
s = 1.59 x 107 mol dm3 [1]
Maximum mass of AgCl that could dissolve
= 1.59 x 107 x 0.200 x 143.5
= 4.56 x 106 g
[1]

(ii)

The concentration of chloride ions from silver chloride in (b)(i) is less than the
square root of the Ksp value of silver chloride. Explain why this is so.
[1]
AgCl(s) Ag+(aq) + Cl(aq)
Cl(aq) from NaCl
caused the above equilibrium to shift left by Le Chateliers Principle.
Thus, the solubility of AgCl is suppressed due to common ion effect. [1]

(iii)

Suggest why when aqueous sodium thiosulfate was added to the resulting
solution in (b)(i), more silver chloride was able to dissolve.
[3]
AgCl(s) Ag+(aq) + Cl(aq)
S2O32 forms a complex with Ag+.
This decreases [Ag+].
[1]

[1]

Hence, the above equilibrium shifts right which causes more AgCl to
dissolve.
[1]
(c)

In 1999, researchers in Israel reported a new type of alkaline battery, called the super
iron battery. This battery used the same anode reaction as an ordinary alkaline battery.
The overall equation for the cell was found to be:
2 FeO42(aq) + 8H2O(l) + 3 Zn(s) 3Zn(OH)2(s) + 2 Fe(OH)3(s) + 4 OH(aq)

Construct
(i)
Construct the half-equations, with state symbols, for each electrode reaction in
alkaline conditions.
[2]
Anode: Zn(s)+2OH(aq) Zn(OH)2(s) + 2e
Cathode: FeO42(aq) + 4H2O (l) + 3e Fe(OH)3 (s) + 5OH(aq)

A is Easy with ADVO!


Tel: (65) 6251 3359 / 8233 2753 www.advoedu.com 1 Goldhill Plaza #02-43 Singapore 308899

Page11

Advo Education Group Pte Ltd

Practice Paper 7

Reg. No. 200710217Z

(c)(ii)

A super-iron battery should last longer than an ordinary alkaline battery of


the same size and weight.
Calculate the quantity of charge released by the reduction of 10.0 g of K 2FeO4 to
Fe(OH)3.
[3]
10.0
= 0.0505 mol
2(39.1) 55.8 4(16)
= 3(0.0505) mol
Q = 3(0.0505) 96500 = 1.46 10 4 C (missing units 1)

Amount of FeO42 =
Amount of e

(iii)

Suggest a reason why the super-iron battery can last longer, given that for a
normal alkaline battery, the reaction at the cathode is:
2MnO2(s) + 2NH4+(aq) + 2e 2NH3(aq) + 2MnO(OH) (s)

[1]

Storage capacity of alkaline batteries are cathode limited and hence


the cathode in the super iron battery accepts 3 moles of electrons/ more
electrons than the normal alkaline battery.
1 FeO42 3e vs 1 MnO2 1e

Page11

A is Easy with ADVO!


Tel: (65) 6251 3359 / 8233 2753 www.advoedu.com 1 Goldhill Plaza #02-43 Singapore 308899

You might also like