6.

Redox Equilibria

A) Redox Reactions
(a) Redox reactions in terms of electron transfer
Oxidation loss of electron(s)
Reduction gain of electron(s)
e.g.(1)

loss of 2 e- (oxidation)
Cu +

Cl2

CuCl2

gain of e- (reduction)
(2)

loss of 2 e- (oxidation)
Zn

Cu2+

Zn2+

Cu

gain of 2 e- (reduction)

(b) Oxidation State (Number)

Rules for Assigning Oxidation State
1. Oxidation state of an atom in an element = 0
e.g. Na

OS = 0

H2

OS = 0

O2

OS = 0

2. The more electronegative atom in a compound has the

ve oxidation state
102

e.g.

NH3

OS of N = -3

NF3

OS of N = +3

3. Sum of oxidation state of a neutral compound = 0

e.g. NaCl (+1) + (-1) = 0

H 2O

(+1 x 2) + (-2) = 0

4. Sum of oxidation state of a simple / complex ion = the

charge on the ion.
e.g. SO42- (-6) + 4(-2) = -2

NH4+ (-3) + 4(+1) = +1

5. Some elements always have the same oxidation state in their

compounds
(i) Group I metals:

+1

(ii) Group II metals: +2

(iii) Al:

+3

(iv) H: +1 in covalent compounds with non-metals

-1 with group I & II metals (e.g. NaH, MgH2)
(v) F: -1
(vi) O: -2 except
1. +2 in OF2
2. 1 in peroxides (e.g. Na2O2, H2O2)
3. 1/2 in superoxides (e.g. KO2)
e.g. POCl3
103

P + (-2) + 3(-1) = 0

P = +5

HPO3-

(+1) + P + 3 (-2) = -2

P = +3

6. Assigning oxidation state to elements in covalent compounds

Oxidation state = formal charge on the atom when the

shared electrons are assigned to the more electronegative

one of the bonded atoms.
e.g.

CH4,

EN of C > H
OS of C = -4

H +1
+1
-1C -1 H
-1 -1

+1
H

OS of H = +1

H +1

N2H4 EN of N > H
+1 H

H
+1

-1 0

0 -1

-1

OS of N = -2

H+1
-1

OS of H = +1

+1

S2O82
-2
O
-2 O

O
-2
104

-1
O

S +6
O
-1

-2
O
S +6
O
-2

O-2

S2O32-

2(S) + 3(-2) = -2

S = +2

+2 is only the average OS of S

S-2

S0
S +4
O
-2

or

+6

O -2
O -2

O -2
O -2

O
-2

more electropositive
owing to its direct
bonding to more
electronegative oxygen
atom

Ex 6.3-1
Try to assign the OS of the underlined elements.
OH

ClO

CO32

ClO3

NH4+

ClO4

CrO4

Cr2O7

S4O62O

MnO4

MnO4

SO

(c) Redox reactions in terms of oxidation number

Oxidation increase in oxidation state

Reduction decrease in oxidation state

105

S
O

O
O

e.g.

+1

oxidation

2Na(s) + Cl2(g) 2NaCl(s)

0
1

reduction

Disproportionation a chemical reaction in which a particular

chemical species is simultaneously oxidized and reduced
e.g.

reduction
3ClO-

+1

2Cl-1

ClO3+5

oxidation

Oxidizing agent- substance which oxidize others but itself being

reduced
Reducing agent substance which reduce others but itself being
oxidized
Oxidizing agent and reducing agent are relative only.

compound may be an oxidizing agent in one reaction but it may

be a reducing agent in another reaction.

106

Ex 6.3-2
Decide whether the following reactions are redox reactions or not and thus identify
the reducing agent and oxidizing agent
i)

5SO32 + 2MnO4 + 6H+ 5SO42 + 2Mn2+ + 3H2O

ii)

Cr2O72 + 2OH 2CrO42 + H2O

iii)

O3 + NO O2 + NO2

iv)

SiCl4 + 2H2O 4HCl + SiO2

v)

2H2O2 2H2O + O2

vi)

3NO2 + H2O 2HNO3 + NO

(d) Balancing Redox Reactions Equations

Half-equation method
Steps:

1. Separate the reaction into two half-equations: oxidation half &

reduction half.
2. Balance each half equation separately:
i)

Balance all elements other than O & H.

ii)

Balance the O by adding an appropriate number of H2O to

the side deficient in O.

107

iii)

In an acidic solution, balance H by adding the appropriate

no. of H+ to the side deficient in H.
In an alkaline solution, balance H by adding the
appropriate no. H2O to the side deficient in H and then add
an equal no. of OH- on the opposite side.

iv) Then balance the charge by adding e(s) to the side deficient
in negative charge.
3. Multiply the two balanced half-equations by appropriate no. so
that the no. of e gained in one half equation is equal to that lost
in the other.
4. Add the 2 half-equations and eliminate the e. Collect like terms
and cancel any duplications on both sides if necessary.

Example
(1) MnO4- + Fe2+ Mn2+ + Fe3+

108

MnO4-

Mn2+

MnO4-

Mn2+ + 4H2O

MnO4- + 8H+

Mn2+ + 4H2O

MnO4- + 8H+ + 5e

Mn2+ + 4H2O(1)

Fe2+

Fe3+

Fe2+

Fe3+ + e

Mn2+ + 4H2O + 5Fe3+

..(2)

(1) + (2) x 5
MnO4- + 8H+ + 5Fe2+

(2) Cr2O72- + SO2 Cr3+ + SO42Cr2O72-

Cr3+

Cr2O72-

2Cr3+

Cr2O72-

2Cr3+ + 7H2O

Cr2O72- + 14 H+

2Cr3+ + 7H2O

Cr2O72- + 14 H+ + 6 e

2Cr3+ + 7H2O..(1)

SO2 + 2H2O

SO42-

SO2 + 2H2O

SO42- + 4H+

SO2 + 2H2O

SO42- + 4H+ + 2e..(2)

(1) + (2) x 3
Cr2O72- + 14 H+ + 3SO2 + 6H2O 2Cr3+ + 7H2O + 3SO42- + 12H+
Cr2O72- + 2H+ + 3SO2

109

2Cr3+ + H2O + 3SO42-

(3) MnO4- + H2O2 MnO2 + O2

(basic)

MnO4-

MnO2

MnO4-

MnO2 + 2H2O

MnO4- + 4H2O

MnO2 + 2H2O + 4OH-

MnO4- + 2H2O + 3e

MnO2 + 4OH- .(1)

H2O2

O2

H2O2 + 2OH-

O2 + 2H2O

H2O2 + 2OH-

O2 + 2H2O + 2e (2)

(1) x 2 + (2) x 3
2MnO4- + 4H2O + 3H2O2 + 6OH- 2MnO2 + 8OH- + 3O2 + 6H2O
2MnO4- + 3H2O2 2MnO2 + 2OH- + 3O2 + 2H2O
(4) SnO22-

Sn + SnO32- (basic)

SnO22-

Sn

+ 2H2O

SnO22- + 4H2O

Sn

+ 2H2O

SnO22- + 2H2O + 2e

Sn

+ 4OH- (1)

SnO22-

SnO32-

SnO22- + H2O

SnO32-

SnO22- + H2O + 2OH-

SnO22- + 2OH-
110

+ 4OH-

SnO32- + 2H2O

SnO32- + H2O + 2e (2)

(1) + (2)
2SnO22-

+ 2H2O + 2OH-

2SnO22-

+ H2O

Sn + 4OH- + SnO32- + H2O

Sn + 2OH- + SnO32-

Ex 6.3-3
Balance the following equations
i)

Cu + NO3 Cu2+ + NO

ii) MnO4 + I Mn2+ + I2

iii) SO32 + Br2 SO42 + Br (acidic)
iv) Mn3+ MnO2 + Mn2+ (acidic)
v) Sn2+ + H2O2 Sn4+ + H2O (acidic)
vi) MnO2 + PbO2 MnO4 + Pb2+ (acidic)
vii) Cl2 Cl + ClO3 (basic)
viii) Cl2 Cl + ClO (basic)
ix) H2O2 + Cr(OH)4- CrO42- + H2O (basic)

B) Electrochemical Cells
(a) Introduction
Redox reaction can be split into two half reversible
111

reactions.
Zn(s)
Cu2+(aq)

Zn2+(aq) + 2e
+ 2e

Cu(s)

Zn(s) + Cu2+(aq)

Zn2+(aq) + Cu(s)

Equilibrium position of the redox reactions

depends on the tendencies of reducing agent or
oxidizing agent to donate or gain electrons.
(b) Single Electrode Potential
When a metal M is placed into a solution containing
Mn+ two opposing reactions may occur:

M
E
e M n+
n+ e
M e
e n+
eM
n+
M e
e M n+
n+e
e
ee
e
e
M n+e e M n+
M M n+M n+

(i) M(s) Mn+(aq) + ne

M n+ (aq)

(oxidation)

Metal M loses electrons & dissolves to form Mn+

(ii) Mn+(aq)

+ ne M(s) (reduction)

Mn+ gains electrons & forms M on the electrode

112

Mn+(aq) + ne

M(s)

At equilibrium: rate of oxidation = rate of reduction

An electrode potential is set up at the interface of the
solid and solution phases single electrode
potential
The position of equilibrium depends on
1. nature of metal / metal ion system,
2. concentration of metal ions,
3. temperature.
Single electrode potential cannot be measured absolutely

c) Electrochemical Cells Made up of Metal / Metal Ions Systems

Made up of 2 different metal / metal ion half cells
Different metal / metal ion half cells will have different

electrode potentials

113

 If we connect an electrical wire between the two different metal

electrodes.
The potential difference will drive electrons through the

conducting wire from one cell to another (but only

instantaneously).
Current will stop after a while as charges would be built up in

the two half cells which prevent further electrons movement.

The problem can be solved by adding a salt bridge or a

porous partition.

It enables electrical contact while

preventing the mixing of solutions which leads to the direct

redox reaction.

Salt bridge contains a strong electrolyte (e.g. saturated KCl,

KNO3 or NH4NO3) held in a jelly like matrix in a inverted

114

Utube or just a piece of filter paper soaked with strong

electrolyte
Porous partition contains tiny passage that allows hindered

flow of ions.
e.g.

Daniell cell (composed of Cu and Zn half cell)

Zn electrode:

Zn(s) Zn2+(aq) + 2e

Cu electrode:

Cu2+(aq) + 2e Cu(s) cathode (+ve pole)

anode (-ve pole)

Electrons flow from Zn electrode through external circuit

to Cu electrode.
Overall reaction:

Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

d) Electromotive Force (e.m.f.) of Electrochemical Cell

Absolute potential of a half cell CANNOT be measured.

115

 Only the potential difference between 2 different half cells can be

measured.
The potential difference of 2 half cells can be measured by the

following circuit.

Potential difference (measured by the voltmeter) increases with

the increasing resistance (decreasing current).

NO current flow maximum potential difference e.m.f. of the

cell

116

e) E.m.f. Measurement of Electrochemical Cell

A voltmeter cannot measure the e.m.f. of an electrochemical cell
accurately because current is taken by voltmeter.
E.m.f. can be measured by:
(1) Use a voltmeter of high resistance (faster method)
e.g. a transistor voltmeter, impedance voltmeter or
a digital multimeter.
(2) A potentiometer
When

no

current

flows

(i.e.

no

galvanometer),

e.m.f. of the cell under measurement =

known e.m.f. of the standard cell

117

distance AD
distance AC

deflection

on

(f)

Cell Diagrams (IUPAC Convention)

Commonly used notations

1. Solid line ()

boundaries between electrodes and

solution (phase boundaries).

2. Dotted line

(M) porous partition

(MM) salt bridge

3. E or Ecell

e.m.f. of a cell in volt.

4. Sign (+ or ) polarity of the RIGHTHAND electrode.

e.g.

Daniell cell
Anode

Cathode

Zn(s) Zn2+(aq) M Cu2+(aq) Cu(s) E = + 1.1 V

Zn(s) Zn2+(aq) Cu2+(aq) Cu(s)
Reaction represented:
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
If the cell diagram is represented as:
Cu(s) Cu2+(aq)M Zn2+(aq) Zn(s)
Cu(s) Cu2+(aq) Zn2+(aq) Zn(s)
Reaction represented:
Zn2+(aq) + Cu(s) Zn(s) + Cu2+(aq)
118

E= 1.1 V

C) Standard Electrode Potential and Electrochemical Series

a) Standard Hydrogen Electrode
Since only potential difference between 2 electrodes
can be measured standard electrode must be
chosen so as to compare electrode potential of
different system.
Standard hydrogen electrode is one of the standard
electrodes and its electrode potential is arbitrarily
assigned as 0.

At equilibrium:

2H+(aq)

+2e

H2(g)

Cell diagram: Pt(s)H2(g, 1 atm)2H+(aq, 1.0 M)MM

Platinum electrode is used as an inert electrode by which

electrons can leave or enter the electrode system.

Platinum

black acts as a catalyst, being porous, it retains a comparatively

119

large quantity of hydrogen.

b) Standard Electrode Potential E

Electrode potential depends on [ion] and temp. Thus we have to

standardize the potential measurement conditions.

E is a value of an electrode potential relative to the standard

hydrogen electrode under the conditions:

1. [ion] = 1.0 M
2. temp. = 298 K
3. pressure of gas = 1 atm.

c) Standard Electrode Potential from e.m.f. Measurements

Standard electrode potential of a metal / metal ion system can be

measured by using standard hydrogen electrode under standard

conditions.
Pt(s)H2(g, 1 atm)2H+(aq, 1.0 M)MM Mn+(aq, 1.0M) M(s)
E = Ecell = ER.H.S. EL.H.S. = ER.H.S.
where ER.H.S..= the electrode to be measured
EL.H.S = the standard Hydrogen electrode = 0
120

 Electrode potential to be measured is always written on R.H.S.

and thus it always refers to the Reduction Potential.

Mn+(aq) + ne

M(s)

The more ve the E, the higher the tendency to release e and

vice versa.

Oxidized form
K+(aq) + e
Ca2+(aq) + 2e
Na+(aq) + e
Mg2+(aq) + 2e
Al3+(aq) + 3e
Zn2+(aq) + 2e
Fe2+(aq) + 2e
Pb2+(aq) + 2e

E / Volts
2.92
2.87
2.71
2.37
1.66
0.76
0.44
0.13

Reduced form
K(s)
Ca(s)
Na(s)
Mg(s)
Al(s)
Zn(s)
Fe(s)
Pb(s)

d) Redox Equilibria Extended to Other Systems

Reduction potential of a redox system other than metal / metal

ion system can also be measured.

Pt is used as an inert

electrode.
e.g.

Br2(aq) + 2e

2Br(aq)

MM Br2(aq), 2Br(aq)Pt(s)
121

Non-metal / non-metal ion

Fe3+(aq)

Fe2+(aq)

Ion / ion

MM Fe3+(aq), Fe2+(aq)Pt(s)
MnO4(aq) + 8H+(aq) + 5e

Mn2+(aq) + 4H2O(l)

MM [MnO4(aq)+ 8H+ (aq)], [Mn2+(aq) + 4H2O(l)Pt(s)

2IO3-(aq) + 12H+(aq) + 10 e

I2(aq) + 6H2O(l)

MM[2IO3-(aq, 1M) + 12H+(aq, 1M)], [I2(aq, 1M) + 6H2O(l)]Pt(s)

Rules for constructing cell diagram of system other than metal

/ metal ion.
1. The reduced form of ions is put nearest to the inert electrode.
2. Reduced form is separated oxidized form by comma
3. For oxidized & reduced forms containing more than one
chemical species, they must be included in the oxidized &
reduced forms of the half cell diagram by square brackets.

122

e) Electrochemical Series
E.C.S. is formed when the electrode potentials of various

redox systems are tabulated together.

The more ve electrode potential are at the TOP

Greater tendency to lose e

Stronger Reducing Agent
123

D) Uses of Standard Reduction Potentials

(a) To construct a working electrochemical cell and calculate its
e.m.f.
Consider the following standard reduction potential at 298 K.
Cu2+(aq) + 2e
Ag+(aq) + e
Zn2+(aq) + 2e

Cu(s)
Ag(s)
Zn(s)

E= +0.337V
E= +0.799V
E = 0.763V

As to construct a working cell, i.e. a cell which runs

spontaneously, the e.m.f. of the cell MUST BE +ve.

Ecell = Eright - Eleft

Case 1:
Cell diagram:
Cu(s)Cu2+(aq 1.0 M) MM Ag+(aq 1.0 M) Ag(s)

E = +0.462V

Ecell = -0.799 (0.337) = +0.462 V

2Ag+(aq) + Cu(s)

124

2Ag(s) + Cu2+(aq)

E = +0.462V

Case 2:
Cell diagram:
Zn(s)Zn2+(aq 1.0 M) MM Cu2+(aq 1.0 M) Cu(s)

E= +1.1V

Ecell = (+0.337) (- 0.763) = + 1.1 V

Cu2+(aq) + Zn(s)

Cu(s) + Zn2+(aq)

E = +1.100V

Ex 6.3-4
When a standard Ni2+(aq)Ni(s) half cell is connected to a standard Cu2+(aq)Cu(s)
half cell, the cell voltage is 0.59 V. The copper electrode is the cathode.
Determine the standard reduction potential for Ni2+(aq)Ni(s) half cell. (Given:
E of Cu2+(aq)Cu(s) = +0.34 V)

125

Ex 6.3-5
A cell is based on the reaction of
5Fe(s) + 2MnO4(aq) + 16H+(aq) 5Fe2+(aq) + 2Mn2+(aq) + 8H2O(l)

Given that:

Fe2+(aq)Fe

E = 0.44 V

MnO4(aq)Mn2+(aq)

E = +1.51 V

a) Write balance equations for the reactions occurring at the cathode

and the anode.
b) State the direction in which electrons move when the electrodes
are connected externally.
c) Calculating the e.m.f. of the cell
d) Write the cell diagram.

126

b) To Predict the Feasibility of Redox Reactions

= +ve energetically feasible

=0

in equilibrium

= -ve

not energetically feasible

E values predicts whether a reaction is energetically feasible or

not, it does not tell the rate at which the reaction takes place.
E is an intensive property, i.e. independent of the amount of

the no. of e transferred.

In using E to predict feasibility of a reaction, care must be taken

that prediction apply only to standard conditions only.

In general, if Ecell> 0.4 V, we can predict with confidence.

Ex 6.3-6
Given that:

Cu2+(aq) + 2e
Ag+(aq) + e

i)

Cu(s)
Ag(s)

E = +0.34 V
E = +0.80 V

Write an ionic equation for the spontaneous reaction

ii) Calculate Ecell

iii) Write the cell diagram for this reaction.
iv) Explain why the e.m.f. measured by a potentiometer differs from that
127

calculated in (iii).

Ex 6.3-7
Given that:

Ag+(aq) + e
AgCl(s) + e

i)

Ag(s)
Ag(s) + Cl(aq)

E = + 0.80 V
E = + 0.22 V

Write the equation for the spontaneous reaction.

ii) Calculate the cell e.m.f.

iii) Write the cell diagram for the spontaneous reaction.

128

Ex 6.3-8
Given that:

Zn2+(aq) + 2e
Hg2Cl2(aq) + 2e

i)

Zn(s)

2Hg(l) + 2Cl(aq) E = +0.28 V

Write an ionic equation for the spontaneous reaction.

ii) Calculate Ecell.

iii) Write the cell diagram for this reaction.

Ex 6.3-9
(a) Given that
Br2(aq) + 2e

E = +1.09 V

2Br-(aq)

O2(g) + 2H2O(l) + 4e

4OH-(aq)

E = +0.40 V

Predict whether Br2 or O2 is a stronger oxidizing agent.

129

E = 0.76 V

(b) Given that:

MnO42(aq) + 4H+(aq) +2e
MnO4(aq) + e

MnO2(s) + 2H2O(l)

E = +2.26 V
E = +0.56 V

MnO42(aq)

Show that MnO42(aq) disproportionate in acidic medium.

Ex 6.3-10
Given that:

i)

S4O62(aq), 2S2O32(aq)Pt(s)

E= +0.10 V

Br2(aq), 2Br(aq)Pt(s)

E = +1.10 V

I2(aq), 2I(aq)Pt(s)

E = +0.55 V

Write the cell diagram for the cell with highest e.m.f. and the equation for the
chemical change that takes place.

130

ii) Which is the positive electrode?

iii) An aqueous solution of I2 oxidizes S2O32(aq) to S4O62(aq), but an aqueous
Br2(aq) oxidizes it further to SO32(aq).
a) What does this tell about the relative oxidizing power of Br2 and I2?
b) What conclusion can you draw about the E of the of the following half
cell?
[2SO32(aq) + 6H+(aq)], [2S2O32(aq) + 3 H2O(l)]Pt(s)

131

E) Effect of Concentration Change on Electrode Potential

Cu(s) Cu2+(aq,1M) M Ag+(aq) Ag(s)

e.g.

Measure Ecell for different concentration of Ag+(aq)

Plot Ecell vs log [Ag+(aq)]
Ecell

+0.46 V

log [Ag+] = -8.8

Log [Ag+]

Cell reaction Cu(s) + 2Ag+(aq)

cell

(a) E

Cu2+(aq) + 2Ag(s)

= EAg - ECu = (+0.8) (+ 0.34) = + 0.46 V

Ag+(aq) + e

Ag(s)

E = + 0.8 V

By Le Chatelier Principle
[Ag+] increase in tendency to form Ag+
equilibrium shifts to LHS
electrode potential of Ag becomes less +ve
Ecell becomes less +ve
132

(b) From the graph Ecell as [Ag+]

consistent with the prediction
And Ecell log [Ag+] EAg log [Ag+]

log [Ag+(aq)] = -8.8

(c) When Ecell = 0

Ecell = 0 equilibrium is established

[Ag+]eqn = 1.6 x 10-9 M
Kc =

[Cu 2+ ]
[Ag + ] 2

1
(1.6 x 10 -9 ) 2

Kc = 4 x 1017 dm3 mol-1

(d) log [Ag+] < -8.8 Ecell = -ve

(e) Nernst Equation

RT
E = E + z F ln [ion]

R - gas constant = 8.31 JK-1 T temp

F Faraday constant

z charge of metal ion

2.3 RT
E = E + z F log10 [ion]

133

0.06
E = E + z log10 [ion]

Ex 6.3-11
Al3+(aq) + 3e
Cu2+(aq) + 2e

Al(s)
Cu(s)

E = -1.66 V

E = +0.337 V

Calculate Ecell if [Cu2+] = 0.1 M & [Al3+] = 0.01M

F) Practical Cell for Electricity Production through Chemical

Reactions
There are basically 3 types of cells and batteries

i)

Primary cells

ii) Secondary cells

iii) Fuel cells
134

i) Primary Cells
CANNOT be recharged.
Most common, convenient and cheapest to use
Produce environmental problems with their disposal after use

e.g. Leclanche (Zinc Carbon) cell

Anode:

Zn container

Cathode:

Graphite

Electrolyte:

NH4Cl and ZnCl2 +

MnO2 (in paste form)
Zn(s) Zn2+(aq) + 2e

Anode:
Cathode:

2NH4+(aq)+2MnO2(s)+2eMn2O3(s)+2NH3(aq)+H2O(l)
Overall: Zn(s) + 2NH4+(aq) + 2MnO2(s)
Zn2+(aq) + Mn2O3(s) + 2NH3(aq) + H2O(l)

Cell diagram: Zn(s)Zn2+(aq)M MnO2(s)Mn2O3(s)C(s)

When a current is drawn for sometimes

NH3(g) & Zn2+ accumulates

Equilibrium shifts to LHS
Ecell drops
135

= +1.50

 When the cell is stored for some time without use

Zn + NH4+ Zn2+ + NH3 + H2 occurs

[NH4+] decreases & eqn shifts to LHS
Ecell drops

e.g. Silver oxide battery

Silver oxide cells look like buttons.
The () electrode (anode) is zinc powder.
The (+) electrode (cathode) is silver oxide.

These materials are tightly compacted powders separated by

a moist paste of silver oxide containing some potassium
hydroxide. Moistened paper serves as the salt bridge.
The cell produces 1.5V.

136

Anode:

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

Ag2O(s) + H2O(l) +2e 2Ag(s) + 2OH(aq)

Cathode:
Overall:

Zn(s) + Ag2O(s) ZnO(s) + 2Ag(s)

The silver oxide cell is small and lasts for a long time. It
also gives a steady current.

However, it is more

expensive than other types of dry cells.

Cell diagram:

Zn(s)ZnO(s)KOH(aq)Ag2O(s)Ag(s)

ii) Secondary Cells

Must be charged up first before it can be used.
Usually rechargeable

e.g. Lead acid accumulator

137

Cathode: Pb coated with PbO2

Anode:

Pb metal

When DISCHARGING
Anode:

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

Cathode:

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

Pb(s)+PbO2(s)+4H+(aq)+2SO42(aq)

Cell rxn:

2PbSO4(s)+2H2O(l)
recharge

Cell diagram:
Pb(s) PbSO4(s) H2SO4(aq) PbO2PbSO4(s) Pb(s)

E = -0.35 V

cell

E = +1.69 V

= +1.69 (-0.35) = + 2.05 V

When the battery is recharged by connecting to an external source,

electrons are forced in the opposite direction

Reverse the cell reaction
It is mainly used in motor cars.

series to give a total of 12 V

Life time: 3-5 years

138

Usually 6 cells are joined in

Ex 6.3-12
The rechargeable nickel-cadmium battery has electrodes
of solid cadmium and solid nickel (IV) oxide, NiO2,
coated on a conductor. When this battery discharges,
solid Cd(OH)2 and solid Ni(OH)2 are formed.
electrolyte is a basic medium of KOH.
Cd(OH)2 Cd

E = -0.76 V

NiO2 Ni(OH)2

E = +0.49 V

The

Given

(a) Write balanced equations for the reactions occurring

at cathode and anode when the battery discharges.
(b) Write the overall cell reaction and find Ecell.
(c) What is the direction of electrons flow when the
battery discharges?
(d) Write the cell diagram by IUPAC convention.
(e) Why is the battery re-chargeable and how, in principle,
this is carried out?

139

iii) Fuel Cells

Differences between fuel cells and electrochemical
cells:
Fuel cell is a primary cell which efficiently converts the chemical

energy into electrical energy without losing to heat, mechanical

linkages
Environmentally friendly
Continuous supply of electrical energy
Open system
Flexible: micro to mega Watts

e.g. Hydrogen-oxygen fuel cell

Fuel (H2) and oxidizing agent (O2) are supplied in a continuous

flow into the anode and cathode compartments respectively.

140

 Porous Ni electrodes act as the electrical conductor and also a

catalyst for the reactions.

Anode:

2H2(g) + 4OH(aq) 4H2O(l) + 4e

Cathode: O2(g) + 2H2O(l) + 4e 4OH(aq)

Overall reaction:

2H2(g) + O2(g) 2H2O(l)

Cell diagram:

Ni(s)H2(g)H2O(l)KOH(aq)O2(g)2OH(aq)Ni(s)
It is used as the energy source in spacecraft and the crew can

drink the water produced during the reaction.

It cannot be used as a source of portable power because of heavy

weight ( 500 lb)

G) Corrosion of Iron and Its Prevention
(a) Chemistry of Rusting
(i) Electrochemical Process Involving in Rusting

141

 Around the edge of water droplet

higher [O2]
act as CATHODE

O2(g) + 2H2O(l) + 4e 4OH(aq)

E = +0.40 V

(turn phenophthalein pink)

At the centre of water droplet

lower [O2]
act as ANODE

Fe(s) Fe2+(aq) + 2e

E = 0.44 V

(turn K3Fe(CN)6 blue)

O2(g) + 2H2O(l) + 2Fe(s) 4OH-(aq) + 2Fe2+(aq) E = +0.84V

cell

is +ve spontaneous reaction

Fe2+(aq) formed in the anodic regions travel to the cathodic regions

where it reacts with the OH produced in the cathodic regions.

Fe2+(aq) + 2OH(aq) Fe(OH)2(s)
Fe(OH)2(s) further react with O2(g) in air

4Fe(OH)2(s) + O2(g) + 2 H2O(l) 4Fe(OH)3(s)

Fe(OH)3(s) Fe2O3 nH2O(s) (rust)

142

ii) Essential Conditions for Rusting

1. Moisture (water)
2. Air (O2)

iii) Factors Increasing the Rusting Rate

1. Low pH because it favours Fe Fe2+ + 2e
2. High temperature
3. Present of dissolved electrolytes e.g. NaCl because
conductivity

b) Prevention of Rusting
i) Application of a protective layer (coating)
Nonmoving objects: Painting, varnishing or coating with

plastic
Moving objects:

Greasing or oiling

ii) Cover with a thin layer of another metal which is resistant to

corrosion
1. Tinplating: By immersing Fe in molten Sn (used to make
143

the can of canned food)

Fe2+(aq)Fe(s)

E = 0.44 V

Sn2+(aq)Sn(s)

E = 0.136V

If coating is scratched further rusting occurs because

Fe (ve pole): Fe(s) Fe2+(aq) + 2e
Sn (+ve pole): O2(g) + 2H2O(l) + 4e 4OH(aq)

2. Zincplating (Galvanizing): By immersing Fe in molten Zn.

Zn2+(aq)Zn(s)

E = 0.76 V

Fe2+(aq)Fe(s)

E = 0.44 V

If coating is scratched NO rusting occurs because

Zn (ve pole): Zn(s) Zn2+(aq) + 2e
Fe (+ve pole): O2(g) + 2H2O(l) + 4e 4OH(aq)

144

Zn protects Fe from rusting by sacrificial protection.

Galvanized

iron is not used for canning food because Zn2+ is poisonous.

3. Chromiumplating, Nickelplating: By electrolysis

iii) Alloying
Stainless steel:

An alloy of Fe with Cr (min. 12%), Ni and

Mn. Cr forms a layer of impermeable and
insoluble oxide layer on surface of alloy
grains.

iv) Sacrificial protection

Use more reactive metals, e.g. Mg as sacrificial anode which

supply e to the iron (cathode) to prevent it from oxidation, e.g.

attach large Mg blocks to the steel of the hull of ship, offshore
oil drilling platform or underground oil tank.

145

v) Cathodic protection
Iron is treated as the cathode and connected to the ve
terminal of a battery. This can inhibit the formation of Fe2+.

iv) Socioeconomic Implications of Corrosion and Prevention

Corrosion of iron can cost much to the society

i) Money spent on:

1. Replacement of the corroded articles
2. Prevention of corrosion
3. Indirect cost, e.g. those for the maintenance of machines,
those due to lost production when machines fail down or
where they are shut down for maintenance. (In 1980 in US,
70 billions US dollars were lost annually because of
corrosion)
ii) Wastage of natural resources.
It is estimated that 1 tonne of steel is converted into rust very
90 sec in Britain and about 40 % of the steel made in US is
used to replace steel lost by rusting.
iii) Inconvenience to human beings and even loss of life.
146

Corrosion results in the formation of cracks and crevices

which weaken the strength of metals
concrete in buildings may fall off
aged vehicles may cause more road accidents
Disadvantages of corrosions are outweighed by the relative

low cost, abundance and ease of extraction

The society should assume a greater responsibility for

corrosion prevention in order to have a greater improvement

of the situation.

HKAL Past Paper Questions

86 IIA 2(b)
88 IA 1(c)
90 IA 2(b), IIA 1(b)
92 IIA 1(c)
94 IA 1(d)(e), IIA 3(a)(i)
96 IIB 6(d)(e)
98 IIA 4(a)
00 IIA 3(d)
02 IA 1(b), IIA 3(b)

147

87 IIA 2(b)
89 IIA 1(b)
91 IA 2(a), IIA 2(b)
93 IA 1(d), IIA 1(c), 3(a)
95 IIA 3(c)
97 IA 2(c), IIA 4(a)(b)
99 IIA 1(b)
01 IA 4(a)(b), IIA 4(a)