PC09 Electrochemistry H2 Chemistry 9729

PC09 Electrochemistry

Part I: Redox

1 What is the oxidation number of the underlined atom in each of the following?

(a) N2 0 (b) NH3 -3 (c) NO2− +3 (d) NO3− +5

(e) N2O +1 (f) N2O5 +5 (g) Au(NO3)3 +5 (h) Na2HPO4 +5

(i) Na3PO3 +3 (j) H2PO4− +5 (k) Cl2 0 (l) ClO4− +7

(m) HClO3 +5 (n) ClF3 +3 (o) SO2 +4 (p) SO3 +6

(q) SOCl2 +4 (r) HSO3− +4 (s) MnCl2 +2 (t) MnO2 +4

(u) MnO4− +7 (v) CrCl2 +2 (w) ZnCrO4 +6 (x) K2Cr2O7 +6

2 Which changes can be regarded as oxidation of bromine?

1 Br2  BrO
2 Br2  BrF

3 Br2  BrI

Problem Solving Skill Set (PS3) for Q2

What is the oxidation number of bromine in each species?

Br2 = 0 BrO = +1 BrF = +1 BrI = 1

A Statements 1, 2 and 3 are correct

B Statements 1 and 2 are correct
C Statements 2 and 3 are correct
D Statement 1 only is correct Ans: B

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PC09 Electrochemistry H2 Chemistry 9729

3 State the oxidation number of the respective atoms in the following

compounds or ions.

Compound/ Ion Structure Oxidation Number of Atom

P4 P: 0
P
P P
H: +1
HCl H Cl
Cl: –1

H N H H: +1
NH3
N: –3
H
H
H: +1
CH4 H C H
C: –4
H

O
O: –2
SO32– O S
S: +4
O

Oa: –2

S2O82– Ob: 1
(peroxodisulfate ion) Oc: 2
S: +6

Ca: 3
H O Br Cb: +3

CH3CONHBr N: 3
H Ca Cb N
Br: +1
H H H: +1

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PC09 Electrochemistry H2 Chemistry 9729

4 For the following reactions,

(i) Identify whether it is a redox reaction.

(ii) Explain your answer in terms of changes in oxidation number.

(a) 2KOH (aq) + H2SO4 (aq)  K2SO4 (aq) + 2H2O (l)

This is not a redox reaction.

None of the elements showed a change in oxidation number.

(b) Fe3+ (aq) + 3OH– (aq)  Fe(OH)3 (s)

This is not a redox reaction.

None of the elements showed a change in oxidation number.

(c) 3H2 (g) + N2 (g)  2NH3 (g)

This is a redox reaction.

The oxidation number of H increased from 0 in H2 to +1 in NH3 and

The oxidation number of N decreased from 0 in N2 to −3 in NH3.

(d) 2CO (g) + O2 (g)  2CO2 (g)

This is a redox reaction.

The oxidation number of C increased from +2 in CO to +4 in CO2 and

The oxidation number of O decreased from 0 in O2 to −2 in CO2.

(e) Cl2 (g) + 2OH– (aq)  Cl– (aq) + ClO– (aq) + H2O (l)
This is a redox reaction.

The oxidation number of Cl increased from 0 in Cl2 to +1 in ClO– and

The oxidation number of Cl decreased from 0 in Cl2 to –1 in Cl–.

Problem Solving Skill Set (PS3) for Q4(e)

What is unusual about this reaction?

Cl in Cl2 is both oxidised and reduced simultaneously. It is a disproportionation
reaction.

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PC09 Electrochemistry H2 Chemistry 9729

5 By writing half equations, give the full balanced equation of following reactions
described.

Problem Solving Skill Set (PS3) for Q5

1. For each question, write skeletal half-equations for reduction and oxidation.
2. Balance skeletal half-equations according to method on Page 9 of lecture notes.
3. Take note the medium in which the reaction is taking place. (acidic/basic?)
4. Write the overall full balanced equation.

(a) BrO3− + I− + H+  Br− + I2

Problem Solving Skill Set (PS3) for Q5(a)

What is the skeletal half-equation for reduction? BrO3−  Br–

What is the skeletal half-equation for oxidation? 2I−  I2
What medium is this reaction taking place in? Acidic

[R] BrO3− + 6H+ + 6e–  Br– + 3H2O

[O] 2I−  I2 + 2e–
Overall BrO3− + 6H+ + 6I−  3I2 + Br− + 3H2O

(b) IO4− + I− + H+  I2 + H2O

[R] 2IO4− + 16H+ + 14e–  I2 + 8H2O

[O] 2I−  I2 + 2e–
Overall IO4− + 8H+ + 7I−  4I2 + 4H2O

(c) CrO42 + S2  CrO2 + S (akaline medium)

[R] CrO42– + 2H2O + 3e–  CrO2– + 4OH–

[O] S2–  S + 2e–
Overall 2CrO42– + 4H2O + 3S2–  2CrO2– + 8OH– + 3S

(d) When copper is added to concentrated nitric(V) acid, a pale blue solution of
Cu2+ is formed. Brown fumes of nitrogen dioxide, NO2 are produced.

[R] NO3− + 2H+ + e–  NO2 + H2O (or) HNO3 + H+ + e–  NO2 + H2O

[O] Cu  Cu2+ + 2e–
Overall Cu + 2NO3− + 4H+  Cu2+ + 2NO2 + 2H2O
(or) Cu + 2HNO3 + 2H+  Cu2+ + 2NO2 + 2H2O
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PC09 Electrochemistry H2 Chemistry 9729

(e) When H2O2 is added to a solution of chromite ion, Cr(OH)63− in alkaline

medium, the solution turned yellow and CrO42− is formed. H2O2 is a weak acid
and forms, HO2−, in alkaline medium. The HO2− is reduced to OH−.
[R] 3HO2− + 3H2O + 6e–  9OH− (can refer to data booklet or by
balancing normally)
[O] 2Cr(OH)63− + 4OH− 2CrO42− + 8H2O + 6e–
Overall 2Cr(OH)63− + 3HO2−  2CrO42− + 5H2O + 5OH−

(f) IO3− + I− + H+ + Cl−  ICl2–

(Note : there are no other Cl containing compounds)
[R] IO3− + 6H+ + 2Cl− + 4e–  ICl2− + 3H2O
[O] I− + 2Cl−  ICl2− + 2e–
Overall IO3− + 2I− + 6 H+ + 6Cl−  3ICl2− + 3H2O

Problem Solving Skill Set (PS3) for Q5(b) and Q5(f)

Are these disproportionation reactions?
No. A disproportionation reaction refers to a reaction where the same substance
is simultaneously reduced and oxidised.
This are comproportionation or symproportionation reactions.
Refer to lecture notes (Appendix section, p25)

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PC09 Electrochemistry H2 Chemistry 9729

6 Balance the following redox equation in acidic medium using the change in
oxidation number method.

V3+ + MnO4–  VO2+ + Mn2+

Problem Solving Skill Set (PS3) for Q6

1. Work out the oxidation numbers of the atoms being oxidised and reduced.
2. Balance the number of atoms that was oxidised or reduced. Work out the number of
electrons lost and gained per mole of species.
3. Balance number of electrons by multiplying the species by suitable factors.
4. Take note the medium in which the reaction is taking place. (acidic/basic?) and add
H+ / OH- to balance the charges.
5. Balance H atoms by adding H2O.

Work out oxidation numbers:

V3+  VO2+
+3 +4

MnO4–  Mn2+

+7 +2

1 mol V3+ lose 1 mol e

1 mol MnO4– gain 5 mol e

1 mol MnO4– react with 5 mol V3+

MnO4- + 5V3++ H2O  Mn2+ + 5VO2+ + 2H+

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PC09 Electrochemistry H2 Chemistry 9729

7 The equations for three reactions are given below.

Cl2(g) + 2H2O(l) + SO2(g)  2HCl(aq) + H2SO4(aq)
Cl2(g) + H2S(g)  2HCl(aq) + S(s)
SO2(g) + 2H2S(g)  2H2O(l) + 3S(s)
What is the correct order of strength of the three reacting gases as reducing
agents?

Strongest Weakest

A chlorine hydrogen sulfide sulfur dioxide

B chlorine sulfur dioxide hydrogen sulfide

C hydrogen sulfide sulfur dioxide chlorine

D sulfur dioxide hydrogen sulfide chlorine Ans: C

Problem Solving Skill Set (PS3) for Q7

1. Write the change of oxidation states of the atoms in the three reacting gases.
2. What reaction does a reducing agent undergo? Oxidation.
3. For each equation, identify which species is the reducing agent.
4. Explain your answer in terms of changes in oxidation number.
5. Rank the three reacting gases in order of decreasing reducing power (ability to
reduce other species).

Cl2(g) + 2H2O(l) + SO2(g)  2HCl(aq) + H2SO4(aq)

0 +4 1 +6
Cl2 is reduced. (oxidation state of Cl decreases from 0 in Cl2 to 1 in HCl)
SO2 is oxidised. (oxidation state of S increases from +4 in SO2 to +6 in H2SO4)
SO2 reduces Cl2. SO2 is the reducing agent.

Cl2(g) + H2S(g)  2HCl(aq) + S(s)

0 2 1 0
Cl2 is reduced. (oxidation state of Cl decreases from 0 in Cl2 to 1 in HCl)
H2S is oxidised. (oxidation state of S increases from 2 in H2S to 0 in S)
H2S reduces Cl2. H2S is the reducing agent.

SO2(g) + 2H2S(g)  2H2O(l) + 3S(s)

+4 2 0
SO2 is reduced. (oxidation state of S decreases from +4 in SO2 to 0 in S)
H2S is oxidised. (oxidation state of S increases from 2 in H2S to 0 in S)
H2S reduces SO2. H2S is the reducing agent.

strongest reducing agent  weakest reducing agent

H2S SO2 Cl2

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PC09 Electrochemistry H2 Chemistry 9729

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

When aqueous hydrogen peroxide, H2O2 is mixed with acidified potassium
dichromate(VI), there is a colour change from orange to green. When aqueous
hydrogen peroxide is added to acidified potassium iodide solution, there is a
colour change from colourless to brown.
The oxidation number of oxygen in H2O2 is 1.
What are the oxidation numbers of oxygen after the reactions with potassium
dichromate(VI) and potassium iodide?

After reaction with After reaction with

potassium dichromate(VI) potassium iodide
A 2 2
B 2 0
C 0 2
D 0 0
Ans: C

Problem Solving Skill Set (PS3) for Q8

1. Use the data booklet and understanding of the colour changes to construct half-
equations for potassium dichromate(VI) and potassium iodide.
2. Since this is a redox reaction, one species must be oxidised, the other must be
reduced. Deduce whether hydrogen peroxide is oxidised or reduced in each scenario
(see data booklet).

Construct the half-equation for Cr2O72– (orange) to Cr3+ (green)

[R] 14H+ + 6e + Cr2O72–  2Cr3+ + 7H2O

From data booklet:

[O] H2O2  O2 + 2H+ + 2e
Oxidation of oxygen in O2 is 0.

Construct the half-equation for iodide (colourless) to iodine (brown)

[O] 2I–  I2 + 2e

From data booklet:

[R] H2O2 + 2H+ + 2e  2H2O
Oxidation of oxygen in H2O is 2.

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PC09 Electrochemistry H2 Chemistry 9729

9 Sodium thiosulfate is used in the textile industry to remove an excess of

chlorine from bleaching processes by reducing it to chloride ions.

S2O32 + 4Cl2 + 5H2O  2HSO4 + 8H+ + 8Cl

In this reaction, how many moles of electrons are supplied per mole of
thiosulfate?

A 1
B 2
C 4
D 8 Ans: D

Problem Solving Skill Set (PS3) for Q9

Use the given overall equation to construct half-equations to solve for the number of
moles of electrons per mole of thiosulfate. Show your working:
Method 1:
Construct the half-equation for S2O32– to HSO4–
S2O32– + 5H2O  2HSO4– + 8H+ + 8e‒
1 mole of thiosulfate loses 8 moles of electrons.

Method 2:
Construct the half-equation for Cl2 to Cl–
Cl2 + 2e–  2Cl–
1 mol of Cl2 gains 2 moles of electrons.
Hence, 4 mol of Cl2 gains 8 moles of electrons from thiosulfate

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PC09 Electrochemistry H2 Chemistry 9729

10 When Fe is reacted with Fe3+(aq) ions, Fe2+(aq) ions are formed. Assuming
the reaction goes to completion, how many moles of Fe and of Fe 3+(aq) would
result in a mixture containing equal numbers of moles of Fe3+(aq) and Fe2+(aq)
once the reaction had taken place?

moles of Fe moles of Fe3+(aq)

A 1 2
B 1 3
C 1 5
D 2 3 Ans: C

Problem Solving Skill Set (PS3) for Q10

1. Write the overall balanced equation for this reaction.
2. Hence, use trial and error method to deduce the initial number of moles of
Fe and Fe3+(aq).

Show your working:

Fe  Fe2+ + 2e
Fe3+ + e  Fe2+ x2
Fe + 2Fe  3Fe
3+ 2+

Fe + 2Fe3+  3Fe2+
Initial amt / mol 1 5 0
Change in amt / mol ‒1 ‒2 +3
Final amt / mol 0 3 3

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PC09 Electrochemistry H2 Chemistry 9729

11 A 25 cm3 sample of 0.20 mol dm3 Ti+NO3 required 25 cm3 of 0.10 mol dm3
acidified KMnO4 to oxidise it to Ti3+ in solution.
What is the oxidation state of the manganese in the reduced form?
A 2 B 3 C 4 D 7
Ans: B

Problem Solving Skill Set (PS3) for Q11

Refer to lecture notes (Section 4.2, p20-21). Show your working below:
Method 1:
Let the unknown oxidation state of Mn be +x.

[O]: Ti+  Ti3+ + 2e

[R]: Mn7+ + 7-x e  Mnx+

n(Ti+) = 0.20 x 0.025 = 0.005 mol

n(KMnO4) = n (Mn7+) = 0.10 x 0.025 = 0.0025 mol

n(e) lost = n (e) gained

 2 (0.005) = (7-x) (0.0025)
 x=3

Method 2:
n(Ti+) = 0.20 x 0.025 = 0.005 mol
n(KMnO4) = 0.10 x 0.025 = 0.0025 mol

Ti+  Ti3+ + 2e
1 mol Ti+ loses 2 mol e

n (e) lost = 2 x 0.005 mol = 0.010 mol

n (e) gained per mol of KMnO4 = 0.010 / 0.0025 = 4

Since the initial oxidation state of Mn is +7, the unknown oxidation number is +3.

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PC09 Electrochemistry H2 Chemistry 9729

12 Ethanedioate ions, C2O42, are oxidised by acidified, aqueous potassium

manganate(VII) according to the equation:
2MnO4 (aq) + 5C2O42- (aq) + 16H+(aq)  2Mn2+(aq) + 10CO2(g) + 8H2O(l)
What volume of 0.020 mol dm-3 potassium manganate(VII) is required to oxidise
completely 1.0 x 10-3 mol of the salt KHC2O4•H2C2O4?
A 20 cm3
B 40 cm3
C 50 cm3
D 125 cm3 Ans: B

Problem Solving Skill Set (PS3) for Q12

Write an ionic equation showing the dissociation of the salt, KHC2O4•H2C2O4.

KHC2O4•H2C2O4 (s)  2C2O42– (aq) + K+ (aq) + 3H+ (aq)

Show your working:

Reacting Ratio:
MnO4– : C2O42– = 2 : 5

1 mol of KHC2O4•H2C2O4 gives 2 mol C2O42–

n(C2O42–) = 2 × 1.0 × 10–3

= 2.000 × 10–3 mol

2
n(MnO4‒) = 5 (2.000 x 10–3)

2
(2.000 x 10–3 )
V(MnO4‒) = 5 0.020
= 0.04000 dm3
= 40.0 cm3

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PC09 Electrochemistry H2 Chemistry 9729

13 The oxidation number of vanadium in a complex ion was determined as follows.

A 0.013 mol sample of the complex was dissolved in aqueous sulphuric acid
and the solution made up to 100 cm 3. A 10 cm3 portion of this solution required
20.8 cm3 of 0.025 mol dm3 KMnO4 to oxidise all the vanadium to the +5 state.
Calculate the original oxidation number of vanadium.
MnO4–+ 8H+ + 5e  Mn2+ + 4H2O
20.8
n(MnO4–) = 1000 × 0.025
= 5.200 × 10–4 mol

[Vanadium salt] = 0.013 ÷ (100/1000)

= 0.1300 mol dm‒3
10
n(Vanadium salt) = 1000 × 0.1300
= 0.001300 mol

1 mol of MnO4– gains 5 mol of electrons

ne– transferred = 5.200 × 10–4 × 5

= 0.002600 mol
0.002600
ne– transferred per mol of vanadium complex = 0.001300

=2
Vanadium lost 2 electrons to become +5

Hence, the original oxidation number = +3

Method 2
Vx+  V5+ + (5-x) e
10
n(Vanadium salt) = 1000 × 0.1300 = 0.001300 mol
n(e) lost = 0.001300 (5-x) mol
20.8
n(MnO4–) = 1000 × 0.025 = 5.200 × 10–4 mol

ne– transferred = 5.200 × 10–4 × 5 = 0.002600 mol

0.001300 (5-x) = 0.002600 mol

5 –x = 2
x=3

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