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COMPLETE PHYSICAL

KIMS A-2
CHEMISTRY 9701/42
Paper 4 A Level Structured Questions OCT-- 2019
1 hour 30 minutes
Total Marks:- 60
Candidates answer on the Question Paper.
Additional Materials: Data Booklet

READ THESE INSTRUCTIONS FIRST

Write your Centre number, candidate number and name on all the work you hand in.
Write in dark blue or black pen.
You may use an HB pencil for any diagrams or graphs.
Do not use staples, paper clips, glue or correction fluid.

Answer all questions.

Electronic calculators may be used.


You may lose marks if you do not show your working or if you do not use appropriate units.
A Data Booklet is provided.

At the end of the examination, fasten all your work securely together.
The number of marks is given in brackets [ ] at the end of each question or part question.

This document consists of 18 printed pages

[Turn over

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(b) E in decreasing order of oxidising power

(a selection only – see also the extended alphabetical list on the previous pages)

Electrode reaction E /V

F2 + 2e– ⇌ 2F– +2.87


2–
S2O8 + 2e –
⇌ 2SO4 2–
+2.01
H2O2 + 2H+ + 2e– ⇌ 2H2O +1.77
MnO4– + 8H+ + 5e– ⇌ Mn2+ + 4H2O +1.52
PbO2 + 4H + 2e+ –
⇌ 2+
Pb + 2H2O +1.47
Cl 2 + 2e– ⇌ 2Cl – +1.36
Cr2O72– + 14H+ + 6e– ⇌ 2Cr3+ + 7H2O +1.33
+
O2 + 4H + 4e –
⇌ 2H2O +1.23
Br2 + 2e– ⇌ 2Br– +1.07
ClO– + H2O + 2e– ⇌ Cl – + 2OH– +0.89

NO + 10H + 8e
3
+ –
⇌ +
NH4 + 3H2O +0.87
NO3– + 2H+ + e– ⇌ NO2 + H2O +0.81
Ag + e+ –
⇌ Ag +0.80
3+
Fe + e –
⇌ Fe 2+
+0.77
I2 + 2e– ⇌ 2I– +0.54
O2 + 2H2O + 4e– ⇌ 4OH– +0.40
2+
Cu + 2e –
⇌ Cu +0.34
SO42– + 4H+ + 2e– ⇌ SO2 + 2H2O +0.17
Sn4+ + 2e– ⇌ Sn2+ +0.15
2–
S4O6 + 2e –
⇌ 2S2O 3
2–
+0.09
2H+ + 2e– ⇌ H2 0.00
Pb2+ + 2e– ⇌ Pb –0.13
2+
Sn + 2e –
⇌ Sn –0.14
Fe2+ + 2e– ⇌ Fe –0.44
2+
Zn + 2e –
⇌ Zn –0.76
2H2O + 2e –
⇌ H2 + 2OH –
–0.83
V2+ + 2e– ⇌ V –1.20
2+
Mg + 2e –
⇌ Mg –2.38
Ca2+ + 2e– ⇌ Ca –2.87
K+ + e– ⇌ K –2.92
1

Q.1 (a) (i) Write the expression for Kw.

.............................................................................................................................................

(ii) Use your expression and the value of Kw in the Data Booklet to calculate the pH of
0.150 mol dm–3 NaOH(aq).

(iii) The pH of a 0.150 mol dm–3 solution of piperidine is 11.9.

HN

piperidine

Suggest why this answer differs from your answer in (c)(ii).

.............................................................................................................................................

.............................................................................................................................................

(iv) How would you expect the basicity of piperidine to compare to that of ammonia?
Explain your reasoning.

.............................................................................................................................................

.............................................................................................................................................
[5]

(b) 20.0 cm3 of 0.100 mol dm–3 HCl was slowly added to a 10.0 cm3 sample of 0.150 mol dm–3
piperidine. The pH was measured throughout the addition.

(i) Calculate the number of moles of HCl remaining at the end of the addition.

moles of HCl = .....................

(ii) Hence calculate the [H+] and the pH at the end of the addition.

pH = .....................

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2

(iii) On the following axes, sketch how the pH will change during the addition of a total of
20.0 cm3 of 0.100 mol dm–3 HCl. Mark clearly where the end point occurs.

14

pH
7

0
0 5 10 15 20
volume HCl added / cm3

(iv) From the following list of indicators, put a tick in the box by the side of the indicator most
suitable for this titration.

pH at which place one tick only


indicator
colour changes in this column

A 0-1
B 3-4
C 11 - 12
D 13 - 14

[6]

[Total: 11]

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3

2(a) (i) Draw a fully labelled diagram of the equipment needed to measure the voltage of an
electrochemical cell consisting of the standard hydrogen electrode and the standard
Cu / Cu2+ electrode.

[4]

(ii) For the cell drawn in (i), calculate the and state which electrode is positive.

= ...................................... identity of the positive electrode ....................................


[1]

(b) A monobasic acid, D, has Ka = 1.23 × 10–5 mol dm–3.

(i) Calculate the pH of a 0.100 mol dm–3 solution of D.

pH = ............................ [2]

(ii) An electrochemical cell similar to the one you have drawn in (c)(i) was set up using a
0.100 mol dm–3 solution of D in the hydrogen electrode instead of the standard solution.

Use the data and the Nernst equation, E = E o + 0.059 log [H+(aq)], to calculate the new E cell
in this experiment.

E cell = ............................ V [2]

[Total: 9]

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4

3 (a) The oxidation of nitrogen(II) oxide is shown in the equation.

2NO(g) + O2(g) → 2NO2(g)

The initial rate of this reaction was measured, starting with different concentrations of the two
reactants. The following results were obtained.

experiment [NO] [O2] initial rate


number / mol dm–3 / mol dm–3 / mol dm–3 s–1

1 0.032 0.012 4.08 × 10–3


2 0.032 0.024 8.15 × 10–3
3 0.064 0.024 3.28 × 10–2
4 0.096 0.036

(i) Use the data in the table to determine the order with respect to each reactant. Show your
reasoning.

.............................................................................................................................................

.............................................................................................................................................

.............................................................................................................................................

.............................................................................................................................................

(ii) Calculate the initial rate in experiment 4. Give your answer to two significant figures.

initial rate = ............................. mol dm–3 s–1

(iii) Write the rate equation for this reaction.

.............................................................................................................................................

(iv) Use the results of experiment 1 to calculate the rate constant, k, for this reaction.
Include the units of k.

rate constant, k = .......................................... units ..........................................


[6]

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5

(b) (i) On the following axes

● draw two Boltzmann distribution curves, at two different temperatures, T1 and T2 (T2 > T1),
● label the curves and the axes.

(ii) State and explain, using your diagram, the effect of increasing temperature on the rate of
reaction.

.............................................................................................................................................

.............................................................................................................................................

.............................................................................................................................................
[5]

[Total: 11]

4 (a) Complete the table using ticks () to indicate whether the sign of each type of energy change,
under standard conditions, is always positive, always negative or could be either positive or
negative.

always always either positive


energy change
positive negative or negative

electron affinity

enthalpy change of atomisation

ionisation energy

lattice energy
[2]

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6
(b) The Born-Haber cycle for magnesium chloride is shown.

Mg2+(g) + 2Cl (g) + 2e–

ΔH5
ΔH4
Mg2+(g) + 2Cl –(g)
Mg+(g) + 2Cl (g) + e–

ΔH3
Mg(g) + 2Cl (g)

ΔH2
Mg(g) + Cl 2(g) ∆H6

ΔH1
Mg(s) + Cl 2(g)

ΔH7
MgCl 2(s)

(i) Explain why ΔH4 is greater than ΔH3.

.............................................................................................................................................

....................................................................................................................................... [1]

(ii) What names are given to the enthalpy changes ΔH6 and ΔH7?

ΔH6 ......................................................................................................................................

ΔH7 ......................................................................................................................................
[2]

(c) Chlorine is in Group 17.

Suggest the trend in the first electron affinity of the elements in Group 17. Explain your answer.

....................................................................................................................................................

....................................................................................................................................................

.............................................................................................................................................. [2]

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7

(d) The equation for the formation of magnesium oxide from its elements is shown.
1
Mg(s) + 2 O2(g) MgO(s) ΔH o = – 602 kJ mol–1

substance S o / J K–1 mol–1


Mg(s) 32.7
O2(g) 205
MgO(s) 26.9

Use the equation and the data given in the table to calculate ΔG o for the reaction at 25 °C.

ΔG o = .............................. units ..............................


[4]

[Total: 9]

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8
5 (a) T
he diagram shows the apparatus used to measure the standard electrode potential, E o, of
Fe3+(aq) / Fe2+(aq).

B D E

C F

(i) Identify what the letters A to F represent.

A ................................................................. D ..............................................................

B ................................................................. E ...............................................................

C ................................................................. F ...............................................................
[3]

(ii) Label the diagram to show

● which is the positive electrode,


● t he direction of electron flow in the external circuit.

Use the Data Booklet to help you.


[1]

(b) I n another experiment, an Fe3+(aq) / Fe2+(aq) half-cell was connected to a Cu2+(aq) / Cu(s)
half-cell.

etermine the standard cell potential,


D , when these two half-cells are connected by a wire
and the circuit is completed.
Use the Data Booklet to help you.

= .............................. V [1]

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9
(c) (i) The E o of Ni2+(aq) / Ni(s) is –0.25 V.

State and explain how the electrode potential changes if the concentration of Ni2+(aq) is
decreased.

.............................................................................................................................................

.............................................................................................................................................

....................................................................................................................................... [1]

(ii) The E o of Cr3+(aq) / Cr2+(aq) is –0.41 V.

Calculate the electrode potential when [Cr3+(aq)] is 0.60 mol dm–3 and [Cr2+(aq)] is
0.15 mol dm–3. Use the Nernst equation.

0.059 [oxidised species]


E = Eo + log
z [reduced species]

E = .............................. V [2]

[Total: 8]

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10
6 (a) Chlorine dioxide undergoes the following reaction in aqueous solution.

2Cl O2 + 2OH– Cl O2– + Cl O3– + H2O

The initial rate of the reaction was measured at different initial concentrations of Cl O2 and OH–.
The table shows the results obtained.

[Cl O2] [OH–] initial rate


experiment
/ mol dm–3 / mol dm–3 / mol dm–3 s–1

1 1.25 × 10–2 1.30 × 10–3 2.33 × 10–4


2 2.50 × 10–2 1.30 × 10–3 9.34 × 10–4
3 2.50 × 10–2 2.60 × 10–3 1.87 × 10–3

(i) U
se the data in the table to determine the rate equation, showing the order with respect to
each reactant. Show your reasoning.

.............................................................................................................................................

.............................................................................................................................................

.............................................................................................................................................

.............................................................................................................................................

.............................................................................................................................................

.............................................................................................................................................

rate equation = ............................................................


[3]

(ii) C
alculate the value of the rate constant, k, using the data from experiment 2. State its
units.

k = .............................. units .............................. [2]

(b) (i) Explain the difference between heterogeneous and homogeneous catalysts.

.............................................................................................................................................

.............................................................................................................................................

....................................................................................................................................... [1]

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11
(ii) Complete the table using ticks () to indicate whether the catalyst used in the reaction is
heterogeneous or homogeneous.

catalysed reaction heterogeneous homogeneous

manufacture of ammonia in the Haber process

removal of nitrogen oxides from car exhausts

oxidation of sulfur dioxide in the atmosphere


[2]

(c) Some reactions are catalysed by one of the products of the reaction. This is called autocatalysis.
An example of autocatalysis is the reaction between acidified manganate(VII) ions, MnO4–,
and ethanedioic acid, (CO2H)2. Mn2+ ions catalyse this reaction. The reaction is slow in the
absence of a catalyst.

(i) Balance the equation for this reaction.

......MnO4– + ......H+ + ......(CO2H)2 ......Mn2+ + ......CO2 + ......H2O


[2]

(ii) The graph shown is a concentration-time graph for a typical reaction.

concentration
of reactant

time

On the axes below, sketch the curve you would expect for the autocatalysed reaction in (i).

concentration
of MnO4–

time
[2]

[Total: 12]

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12

Standard electrode potential and redox potentials, E⦵ at 298 K (25 °C)

For ease of reference, two tables are given:


(a) an extended list in alphabetical order
(b) a shorter list in decreasing order of magnitude, i.e. a redox series.

(a) E in alphabetical order


Electrode reaction E /V

Ag+ + e– ⇌ Ag +0.80

Al 3+ + 3e– ⇌ Al –1.66

Ba2+ + 2e– ⇌ Ba –2.90


Br2 + 2e –
⇌ 2Br –
+1.07
2+
Ca + 2e –
⇌ Ca –2.87
Cl 2 + 2e– ⇌ 2Cl – +1.36
2HOCl + 2H+ + 2e– ⇌ Cl2 + 2H2O +1.64

ClO + H2O + 2e –
⇌ –
Cl + 2OH –
+0.89
Co2+ + 2e– ⇌ Co –0.28
Co3+ + e– ⇌ Co2+ +1.82
2+
[Co(NH3)6] + 2e –
⇌ Co + 6NH3 –0.43
Cr2+ + 2e– ⇌ Cr –0.91
Cr3+ + 3e– ⇌ Cr –0.74
3+
Cr + e –
⇌ Cr 2+
–0.41
Cr2O72– + 14H+ + 6e– ⇌ 2Cr3+ + 7H2O +1.33
+
Cu + e –
⇌ Cu +0.52
2+
Cu + 2e –
⇌ Cu +0.34
Cu2+ + e– ⇌ Cu+ +0.15
2+
[Cu(NH3)4] + 2e –
⇌ Cu + 4NH3 –0.05
F2 + 2e– ⇌ 2F– +2.87
Fe2+ + 2e– ⇌ Fe –0.44
3+
Fe + 3e –
⇌ Fe –0.04
Fe3+ + e– ⇌ Fe2+ +0.77
[Fe(CN)6]3– + e– ⇌ [Fe(CN)6]4– +0.36
Fe(OH)3 + e –
⇌ Fe(OH)2 + OH –
–0.56
2H+ + 2e– ⇌ H2 0.00
2H2O + 2e –
⇌ H2 + 2OH –
–0.83
I2 + 2e –
⇌ 2I –
+0.54

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13

Electrode reaction E /V

K+ + e– ⇌ K –2.92
Li+ + e– ⇌ Li –3.04
Mg2+ + 2e– ⇌ Mg –2.38
2+
Mn + 2e –
⇌ Mn –1.18
Mn3+ + e– ⇌ Mn2+ +1.49
MnO2 + 4H + 2e + –
⇌ 2+
Mn + 2H2O +1.23
MnO4 + e – –
⇌ MnO4 2–
+0.56
MnO4– + 4H+ + 3e– ⇌ MnO2 + 2H2O +1.67

MnO + 8H + 5e
4
+ –
⇌ 2+
Mn + 4H2O +1.52
NO3– + 2H+ + e– ⇌ NO2 + H2O +0.81
NO3– + 3H+ + 2e– ⇌ HNO2 + H2O +0.94

NO3 + 10H + 8e + –
⇌ +
NH + 3H2O
4 +0.87
Na+ + e– ⇌ Na –2.71
Ni2+ + 2e– ⇌ Ni –0.25
[Ni(NH3)6] + 2e 2+ –
⇌ Ni + 6NH3 –0.51
H2O2 + 2H+ + 2e– ⇌ 2H2O +1.77

HO2 + H2O + 2e –
⇌ 3OH –
+0.88
O2 + 4H + 4e + –
⇌ 2H2O +1.23
O2 + 2H2O + 4e– ⇌ 4OH– +0.40
O2 + 2H + 2e + –
⇌ H2O2 +0.68
O2 + H2O + 2e– ⇌ HO2– + OH– –0.08
Pb2+ + 2e– ⇌ Pb –0.13
4+
Pb + 2e –
⇌ Pb 2+
+1.69
PbO2 + 4H+ + 2e– ⇌ Pb2+ + 2H2O +1.47
SO42– + 4H+ + 2e– ⇌ SO2 + 2H2O +0.17
2–
S2O8 + 2e –
⇌ 2SO 4
2–
+2.01
S4O62–+ 2e– ⇌ 2S2O32– +0.09
2+
Sn + 2e –
⇌ Sn –0.14
4+
Sn + 2e –
⇌ Sn 2+
+0.15
V2+ + 2e– ⇌ V –1.20
3+
V +e –
⇌ V2+
–0.26
VO2+ + 2H+ + e– ⇌ V3+ + H2O +0.34
VO2+ + 2H+ + e– ⇌ VO2+ + H2O +1.00

VO3 + 4H + e + –
⇌ 2+
VO + 2H2O +1.00
Zn2+ + 2e– ⇌ Zn –0.76

All ionic states refer to aqueous ions but other state symbols have been omitted.

Zafar Iqbal Ch.


14

(b) E in decreasing order of oxidising power


(a selection only – see also the extended alphabetical list on the previous pages)

Electrode reaction E /V

F2 + 2e– ⇌ 2F– +2.87


2–
S2O8 + 2e –
⇌ 2SO4 2–
+2.01
H2O2 + 2H+ + 2e– ⇌ 2H2O +1.77

MnO + 8H + 5e
4
+ –
⇌ Mn + 4H2O2+
+1.52
PbO2 + 4H + 2e + –
⇌ 2+
Pb + 2H2O +1.47
Cl 2 + 2e– ⇌ 2Cl – +1.36
Cr2O72– + 14H+ + 6e– ⇌ 2Cr3+ + 7H2O +1.33
O2 + 4H + 4e + –
⇌ 2H2O +1.23
Br2 + 2e– ⇌ 2Br– +1.07

ClO + H2O + 2e –
⇌ –
Cl + 2OH –
+0.89

NO + 10H + 8e
3
+ –
⇌ +
NH4 + 3H2O +0.87
NO3– + 2H+ + e– ⇌ NO2 + H2O +0.81
Ag + e+ –
⇌ Ag +0.80
Fe3+ + e– ⇌ Fe2+ +0.77
I2 + 2e– ⇌ 2I– +0.54
O2 + 2H2O + 4e– ⇌ 4OH– +0.40
2+
Cu + 2e –
⇌ Cu +0.34
SO42– + 4H+ + 2e– ⇌ SO2 + 2H2O +0.17
4+
Sn + 2e –
⇌ Sn 2+
+0.15
2–
S4O6 + 2e –
⇌ 2S2O 3
2–
+0.09
2H+ + 2e– ⇌ H2 0.00
2+
Pb + 2e –
⇌ Pb –0.13
2+
Sn + 2e –
⇌ Sn –0.14
Fe2+ + 2e– ⇌ Fe –0.44
2+
Zn + 2e –
⇌ Zn –0.76
2H2O + 2e– ⇌ H2 + 2OH– –0.83
V2+ + 2e– ⇌ V –1.20
2+
Mg + 2e –
⇌ Mg –2.38
Ca2+ + 2e– ⇌ Ca –2.87
K +e+ –
⇌ K –2.92

Zafar Iqbal Ch.


DATA SHEET
The Periodic Table of the Elements
Group
I II III IV V VI VII 0
1 4
H He
Hydrogen Helium
1 2

7 9 11 12 14 16 19 20
Li Be B C N O F Ne
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon
3 4 5 6 7 8 9 10

23 24 27 28 31 32 35.5 40
Na Mg Al Si P S Cl Ar
Sodium Magnesium Aluminium Silicon Phosphorus Sulphur Chlorine Argon
11 12 13 14 15 16 17 18

39 40 45 48 51 52 55 56 59 59 64 65 70 73 75 79 80 84
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36

85 88 89 91 93 96 101 103 106 108 112 115 119 122 128 127 131

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54

133 137 139 178 181 184 186 190 192 195 197 201 204 207 209
15

Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Caesium Barium Lanthanum Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury Thallium Lead Bismuth Polonium Astatine Radon
55 56 57 * 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86

226 227
Fr Ra Ac
Francium Radium Actinium

Zafar Iqbal Ch.


87 88 89 †

140 141 144 150 152 157 159 162 165 167 169 173 175
*58-71 Lanthanoid series
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
†90-103 Actinoid series Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium
58 59 60 61 62 63 64 65 66 67 68 69 70 71
a a = relative atomic mass 232 238
Key X X = atomic symbol Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium
b b = proton (atomic) number 90 91 92 93 94 95 96 97 98 99 100 101 102 103

The volume of one mole of any gas is 24 dm3 at room temperature and pressure (r.t.p.).