Chapter 12: Oxidation and reduction

Chapter 12: Oxidation and reduction

Practice exercises
12.1

Cu(s) + Cl2(g) CuCl2(s)

Copper is oxidised and is therefore the reducing agent.
Chlorine is reduced and is therefore the oxidising agent.

12.3
Sn in SnCl2 is oxidised and therefore SnCl2 is the reducing agent.
As in H3AsO4 is reduced and therefore H3AsO4 is the oxidising agent.
12.5

3Sn2+ + 16H+ + 2TcO4 2Tc4+ + 8H2O + 3Sn4+

12.7

2MnO4 + 3C2O42 + 4OH 2MnO2 + 6CO32 + 2H2O

12.9

=0.74 V

12.11

Eocell = 0.29. As Eocell is positive, this prediction is correct.

12.13

G = 115.8 kJ

12.15

o
cell

= 1.04 V

12.17 Cd(II) has the highest reduction potential, so we expect it to be reduced to Cd(s) at the
cathode.

Review questions
12.1

(a)
(b)

Oxidation is the loss of one or more electrons. Reduction is the gain of one
or more electrons.
The oxidation number decreases in a reduction and increases in an oxidation.

12.3

The number of electrons involved in both the reduction and the oxidation must be the
same; only those electrons that come from the reducing agent and go to the oxidising
agent are involved. No electrons from external or uninvolved sources are involved
and there cannot be any electrons left unaccounted for at the end. An oxidising agent
is the species that is reduced or gains electrons in an oxidation/reduction reaction. A
reducing agent is the species that is oxidised or loses electrons in an oxidation/
reduction reaction.

12.5

Manganese is reduced. This change in oxidation number requires that manganese

gains three electrons.

12.7

These equations are not balanced since the net charge is different on each side of the
arrow. Balancing gives:
(a)
(b)
(c)
(d)

2Na + Fe2+ 2Na+ + Fe

3Ag+ + Cr 3Ag + Cr3+
3Ag + Au3+ 3g+ + Au
3Ca + 2Al3+ 3Ca2+ + 2Al
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Chemistry 3e by Blackman et al.

12.9

(a)
(b)

Reduction
Oxidation

12.11 A galvanic cell is one in which a spontaneous redox reaction occurs producing
electricity.
A half-cell consists of either the cathode or the anode, together with the
accompanying electrolyte.
12.13 These must be kept separate otherwise Ag+ ions are reduced directly by Cu metal and
no external current is produced.
12.15 Electrolytic conduction is the flow of positive and negative ions. Metallic conduction
is the flow of electrons.
12.17 Net ionic equation: Fe + 2Ag+ Fe2+ + 2Ag
Iron metal is oxidised at the anode and silver ions are reduced at the cathode to silver
metal. The anode half-cell is an iron wire dipping into a solution of Fe2+ ions and the
cathode half-cell is a silver wire dipping into a solution of Ag+ ions. Additionally a
salt bridge connects the two half-cell compartments.
12.19

Silver is reduced because it has a more positive Eo than tin. The standard cell notation
is Ag(s)|Ag+(aq) || Sn2+(aq) | Sn

12.21 A potential is the measure of the electron flow through an external circuit. The unit of
potential is the volt.
12.23

Eocell = Eosubstance reduced Eosubstance oxidised

o
o
o
E cell = E reduction E oxidation

12.25 The standard hydrogen electrode is shown in figure 12.12 of the text. It consists of a
platinum wire in contact with a solution of [H+] equal to 1 M and an atmosphere of

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12.2

Chapter 12: Oxidation and reduction

hydrogen gas at a pressure of 1.013 105 Pa. The standard reduction potential is 0 V
by convention.
12.27 The difference between the reduction potentials for hydrogen and cadmium is a
constant that is independent of the choice of the reference electrode. Hence, the
reduction half-cell potential for cadmium is 0.40 units higher than for hydrogen,
regardless of the chosen reference. If Eo for cadmium is taken to be 0 V, then Eo for
hydrogen is 0.40 V.
12.29 A nonoxidising acid is one in which the H+ ion is the stronger oxidising agent, that
is, the anion is not a better oxidising agent than H+. Examples are HCl and H2SO4.
The oxidising agent of a nonoxidising acid is H+.
12.31 The metal must be below hydrogen (more negative) in the activity series in order for
it to react with HCl.
12.33 Any metal lower in table 12.1 (more reactive) than water (Eo = 0.83 V), for example:
2Na(s) + 2H2O(l) 2NaOH(aq) + H2(g)
2K(s) + 2H2O(l) 2KOH(aq) + H2(g)
2Li(s) + 2H2O(l) LiOH(aq) + H2(g)
12.35

Eocell =

0.0592
log Kc
n

12.37
Ecell = Eocell

0.0592
log Q
n

(Note: The factor 2.303 is required to convert from a natural log to a base 10 log.)
12.39 Rust is iron oxide hydroxide, FeO(OH), that is formed by the reaction of iron with
oxygen in the presence of water. Rusting of iron is a three-step process. Firstly, iron
hydroxide, Fe(OH)2, is formed by the reaction:
2Fe + O2 + 2H2O 2Fe(OH)2
Fe(OH)2 is then oxidised to Fe(OH)3:
4Fe(OH)2+ O2 + 2H2O 4Fe(OH)3
And finally, FeO(OH) is formed by dehydration of Fe(OH)3:
Fe(OH)3 FeO(OH) + H2O
12.41 Passivation is a phenomenon shown by some elements, for example, aluminium and
zinc, which are stable to air, although their reduction potentials are strongly negative.
These metals form an impermeable layer of metal oxide that is stable over a wide pH
range, which covers a corrosive metal and protects it from oxidation.
12.43 In an electrolytic cell, the cathode is negative and the anode is positive. The opposite
is true for a galvanic cell. An inert electrode is an electrode which does not take part
in an electrochemical reaction.
12.45 In solid NaCl, the ions are located in a rigid 3-dimensional lattice. In molten NaCl,
the crystal lattice of the solid has been destroyed and the ions are free to move and
conduct electricity by migrating to either the anode or the cathode:

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Chemistry 3e by Blackman et al.

anode:
cathode:
net:

2Cl(l) Cl2(g) + 2e
Na+(l) + e Na(s)
2Na+(l) + 2Cl(l) 2Na(s) + Cl2(g)

12.47 Reduction of water occurs at the cathode and the pH increases due to the formation of
OH(aq). At the anode, oxidation of water occurs and the pH decreases due to the
production of H+(aq). The overall change in pH is 0 since the amount of H+ formed
and the amount of OH formed are equal. K2SO4 serves as charge balance in the
overall electrolysis process.
12.49 The deposition of 0.10 mol of Au from a Au3+ solution takes longer than the
deposition of 0.10 mol Cu from a Cu2+ solution because the Au3+ requires 1.5 times as
many electrons for deposition than does Cu2+. This is due to the difference in charges
on the ions.
12.51

anode:
Pb(s) + SO42(aq) PbSO4(s) + 2e
cathode:
PbO2(s) + 4H+(aq) + SO42(aq) + 2e PbSO4(s) + 2H2O(l)
6 cells must be connected in series to obtain a potential of 12 V.

12.53 anode:
cathode:

PbSO4(s) + 2H2O(l) 2e + PbO2(s) + 4H+(aq) + SO42(aq)

PbSO4(s) + 2e Pb(s) + SO42(aq)

12.55

anode:
cathode:

Zn(s) + 2OH(aq) ZnO(s) + H2O(l) + 2e

2MnO2(s) + H2O(l) + 2e Mn2O3(s) + 2OH(aq)

12.57

The hydrogen is absorbed by the alloy, Mg2Ni. The electrolyte is KOH.

12.59 The electrode materials in a typical lithium cell are graphite and cobalt oxide. When
the cell is charged, Li+ ions migrate to the graphite. When the cell discharges, the Li+
ions migrate back to the cobalt oxide and the electrons move through the external
circuit to maintain charge balance.

Review problems
12.61

(a)
(b)
(c)
(d)
(e)
(f)
(g)
(h)
(i)

substance reduced (and oxidising agent): HNO3

substance oxidised (and reducing agent): H3AsO3
substance reduced (and oxidising agent): HOCl
substance oxidised (and reducing agent): NaI
substance reduced (and oxidising agent): KMnO4
substance oxidised (and reducing agent): H2C2O4
substance reduced (and oxidising agent): HNO3
substance oxidised (and reducing agent): S
substance reduced (and oxidising agent): H2SO4
substance oxidised (and reducing agent): Fe
substance reduced (and oxidising agent): H2O
substance oxidised (and reducing agent): Na
substance reduced (and oxidising agent): K2Cr2O7
substance oxidised (and reducing agent): CH3CH2OH
substance reduced (and oxidising agent): HNO3
substance oxidised (and reducing agent): I2
substance reduced (and oxidising agent): NaClO4
Substance oxidised (and reducing agent): HCl

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12.4

Chapter 12: Oxidation and reduction

12.63 In the forward reaction, Cl2 undergoes disproportion. One chlorine atom is reduced to
Cl and the other is oxidised to Cl+ (in HOCl). In the reverse reaction, HOCl is the
oxidising agent and Cl is the reducing agent.
12.65
Cl2 is reduced to Cl (oxidising agent)
ClO2 is oxidised to ClO2 (reducing agent)
12.67 (a)

12.69

2CrO42 + 3S2 + 4H2O 2CrO2 + 3S + 8OH

(b)

3C2O42 + 2MnO4 + 4H2O 6CO2 + 2MnO2 + 8OH

(c)

4ClO3 + 3N2H4 4Cl + 6NO + 6H2O

(d)

NiO2 + 2Mn(OH)2 Ni(OH)2 + Mn2O3 + H2O

(e)

3SO32 + 2MnO4 + H2O 3SO42 + 2MnO2 + 2OH

(f)

2 CrO42 + 4H2O + 6 SO42 2CrO2 + 3 S2O82 + 8OH

(g)

2 CrO42 + H2O + 3 SO32 2CrO2 + 3 SO42 + 2OH

(h)

N2H4 + 2 O2 N2 + 2H2O2

(i)

4Fe(OH)2 + O2 + 2H2O 4Fe(OH)3

(j)

Net: 4Au + 16CN + 3O2 + 6H2O 4[Au(CN)4] + 12OH

(a)
(b)

12.71 (a)
(b)
(c)
(d)
(e)
(f)
(g)
(h)
(i)
(j)
(k)
(l)

3Ag + 4HNO3 3AgNO3 + 2H2O + NO

Ag + 2HNO3 AgNO3 + H2O + NO2
NR
2Cr + 3Pb2+ 3Pb + 2Cr3+
NR
3Ag + Au3+ Au + 3Ag+
NR
Mg(s) + Co2+ Mg2+ + Co(s)
2Cr(s) + 3Sn2+ 2Cr3+ + 3Sn(s)
Ni2+ + 2Na Ni + 2Na+
Cr + 3H+ Cr3+ + 3/2H2
NR
Zn + Co2+ Co + Zn2+
2K + 2H2O 2K(OH)2 + H2

12.73 Pt(s) | H2 (1 105 Pa) | H+ (1 M) || Cu2+ (0.5 M) | Pt(s)

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Chemistry 3e by Blackman et al.

12.75

(a)
(b)
(c)
(d)
(e)
(f)
(g)
12.77

Eocell = 0.88 V
Eocell = 1.40 V
Eocell = 2.02 V
Eocell = 0.29 V
Eocell = +0.19 V
Eocell = +0.90 V
Eocell =0.37 V

spontaneous
not spontaneous
spontaneous
not spontaneous
spontaneous
spontaneous
not spontaneous

2 (2HOCl(aq) + 2H+(aq) + 2e Cl2(g) + 2H2O)

3H2O + S2O32(aq) 2H2SO3(aq) + 2H+(aq) + 4e
4HOCl(aq) + 4H+(aq) + 3H2O + S2O32(aq)
2Cl2(g) + 4H2O + 2H2SO3(aq) + 2H+(aq)

reduction
oxidation
net reaction

This simplifies to:

4HOCl(aq) + 2H+(aq) + S2O32(aq) 2Cl2(g) + H2O + 2H2SO3(aq)
12.79

(a)

Eocell = 0.54 V

(b)

Go = 521.0 kJ

(c)

Kc = 2.15 1091

12.81

Ecell = 2.06 V

12.83

Ecell = 0.75 M

12.85

(a)
(b)
(c)

12.87

2.68 g Fe(OH)2

12.89

51.5 hr

12.91

66.2 A

12.93

(a)

2400 C, equivalent to 0.025 moles of electrons.

12 000 C, equivalent to 0.124 moles of electrons.
32 400 C, equivalent to 0.336 moles of electrons.

Possible anode reactions:

2H2O
O2(g) + 4H+(aq) + 4e
2
2SO4
S2O82 + 2e
Anode reaction: 2H2O

(b)

O2(g) + 4H+(aq) + 4e (least negative Eo)

Possible anode reactions:

2H2O
O2(g) + 4H+(aq) + 4e

2Br
Br2 + 2e
Anode reaction: 2Br

Eo = 1.23 V
Eo = 2.01 V

E = 1.23 V
Eo = 1.07 V

Br2 + 2e (least negative Eo)

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12.6

Chapter 12: Oxidation and reduction

(c)

Possible anode reactions:

2H2O
O2(g) + 4H+(aq) + 4e
2Br
Br2 + 2e
2
2SO4
S2O82 + 2e
Anode reaction: 2Br

Eo = 1.23 V
Eo = 1.07 V
Eo = 2.01 V
o

Br2 + 2e (least negative E )

Additional exercises
12.95

Increasing ease of oxidation: Cu Fe Pb Al.

The second and fifth experiments are not required to establish this order.

12.97

50.23 g

12.99 1.54 V
12.101 Charge per e = 1.64 1019 C per electron
12.103 (a)
(i)
(ii)
(iii)

0.06 V
1.62 x 105 J
2.6 1028

Eocell

(b)

Ecell =

(c)

0.09 V

6
5

Mn 2+ ClO3
RT

ln
MnO 6 Cl 5 H + 18
nF
4

12.105 The half-reactions are:

Ag(s) Ag+(aq) + e
Fe3+(aq) + e Fe2+(aq)

anode
cathode

Eo = 0.80 V
Eo = 0.77

Eocell = 0.03 V
Ecell = 0.42 V
The equation for the spontaneous cell reaction is:
Ag+ (aq) + Fe2+(aq) Fe3+ (aq) + Ag(s)
12.107 2.813 103 C
12.109 7.94 hr

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12.7