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Practice Paper 7
(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
A2 + 2Na+ + 2H2O
2NaOH + H2A
0.0025
1000 0.0333 mol dm3
25 50
A2 + H2O
K b1
HA + OH
[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
Page11
Practice Paper 7
(a)
(iv)
pH
12.0
9.38
6.23
1.89
1.44
12.5 25.0
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
Page11
Practice Paper 7
(b)
(ii)
(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
Page11
Practice Paper 7
[1m] each
Reaction
1. 1 mole of geraniol
decolourises 2 moles
of Br2(aq)
Type of reaction
electrophilic addition
oxidative cleavage
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
Practice Paper 7
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
Practice Paper 7
(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
Practice Paper 7
(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)
(ii)
(c)
(i)
(ii)
VO2+ + H2O
(iii) This helps to maintains electrical neutrality (prevent build up of charges in the two
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Page11
Practice Paper 7
(e)
(i)
(ii)
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)
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]
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(a)
Practice Paper 7
(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
Given that,
AgCl(s) + e
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)
[1]
[1]
Page11
Practice Paper 7
(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)
Page11
Practice Paper 7
(c)(ii)
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]
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