PRE UNIVERSITI

SEMESTER 2
CHAPTER 2
ELECTROCHEMISTRY

2.1 Oxidation number

Oxidation numbers are a convenient way of
determining if a substance has been oxidised or
reduced. These numbers are assigned arbitrarily to
atoms and are equal to the charge the atom would
have if its bonds were purely ionic.
1. All free atoms in element have an oxidation
H20 =
P4 =
Na number
=0
Mg
=0
0 zero
0 Cl2 =
of

2. For simple ions (and ionic compounds), the oxidation

32K+ number
=+1 Cais2+the
= same
B3+ =+3
P
=
O
=
F
= 1
+2

3
as the charge of ion

3. For covalent compounds, the covalent bonds are

changed into ionic bonds by assuming that the

bonded electrons are on the more electronegative
atom. Table below shows some elements oxidation
number
Oxidation
Element
Notes
number
Group I
+1
--Group 2
+2
True only to halogen without
Group 17
1
O in it
Exception : 1 for peroxide
and
Oxygen
2
+2 for F2O
Except : metal hydride MH (H
Hydrogen
+1
= -1)

3. In a neutral molecule, the sum of the oxidation

numbers of all atom are equals
1C+2O=0
2 Na + O = 0
2B+3O=0
Na2O2(Na) + (-2) = 0 B2O32(B) + 3(-2) = 0 CO2 1(C) + 2(-2) = 0
C = +4
Na = +1
B = +3
1S + 3O = 0
2Cl + 7O = 0
1H + 1F = 0
SO3 1(S) + 3(-2) = 0 Cl2O72(Cl) + 7(-2) = 0 HF 1(F) + 1(+1) = 0
S = +6
Cl = +7
F = -1
1S + 2H = 0
1N + 3H = 0
1C + 4H = 0
H2S 1(S) + 2(+1) = 0 NH3 1(N) + 3(+1) = 0 CH4 1(C) + 4(+1) = 0
S = -2
N = -3
N = -4
2H + 1C + 3O = 0
2(+1) +1C + 3(-2) = 0
H2CO3 C = +4

2H + 1S + 4O = 0
2(+1) +1S + 4(-2) = 0
H2SO4 S = +6

1H + 1Br + 3O = 0
1(+1) +1Br + 3(-2) = 0
HBrO3 Br = +5

4. In a molecular ion, the sum of the oxidation

numbers of all atoms in the formula unit equals to
the charge on the ion.
CrO4Cr2O72MnO41 Cr + 4 O = -1
1 Cr + 4(-2) = -1
Cr = +7

2 Cr + 7 O = -2
2 Cr + 7 (-2) = -2
Cr = +6

1 Mn + 4 O = -1
1 Mn + 4(-2) = -1
Mn = +7

C2O42-

ClO2-

HSO4-

2 C + 4 O = -2
2 C + 4(-2) = -2
C = +3

1 Cl + 2 O = -1
1 Cl + 2 (-2) = -1
Cl = +3

1 H + 1 S + 4 O = -1
1(+1) + 1S + 4(-2) = -1
S = +6

2.2

Half equation and redox reaction.

Half equation ~ equation which shows how
electrons are accept / donate in a chemical
reaction
donated
When a substance
right
is oxidise, electron is
. ; e- is written at the received
.. side
equation. left
When a substance is reduce, electron is
. ; e- is written as the side
equation.
Oxidatio
Simple half
Reaction
n no
Reaction
Half equation
equation
: State the changes
of oxidation
number change
and write the half equation.
+
0

+1
oxidation
Na

Na
+
e
+
Na Na
Mg Mg

2+

0 +2 oxidation Mg Mg2+ + 2 e-

Al Al3+

0 +3 oxidation Al Al3+ + 3 e-

Cu2+ Cu

+2 0 reduction Cu2+ + 2 e- Cu

Oxi. no
Reaction
Reaction
change
H2 H+

0 +1 oxidation

Cl2 Cl- 0 -1

Half equation
H2 2 H+ + 2 e-

reduction

Cl2 + 2 e- 2 Cl

I- I2

-1 0

oxidation

2 I- I2 + 2 e -

O2 O2-

0 -2

reduction

O2 + 4 e- 2 O2

Fe2+
Fe3+

+2 +3 oxidation

Fe2+ Fe3+ + e-

Pb4+
Pb2+

+4 +2 reduction

Pb4+ + 2 e- Pb2+

 When it comes to the reaction involving molecular

ion, the overall charge has to be balanced in such

order.
1. Write a skeleton half equation. Determine the
reaction (oxidation or reduction) using oxidation
number
2. Balance the charge by adding electrons at the
appropriate side
3. Balance the number of atoms other than oxygen.
4. Based on the changes in number of oxygen, write
the number of water molecule formed/used.
5. From the number of water molecule formed/used,
write the number of hydrogen ion (H+) required.

a) ClO3

in OS : +5 -1 ; reduction
ClChanges

Different in OS = 6, so 6 e- at the LHS of equation

ClO3- + 6 e- ClClO3- + 6 e- Cl- + 3 H2O
6 H+ + ClO3- + 6 e- Cl- + 3 H2O

+
6
H
+
ClO
+
6
e

Cl
+ 3 H2O
3
Half equation :

Changes in OS : +6 +3 ; reduction
Different in OS = 3, so 3 e- at the LHS of equation
b) CrO42- Cr3+

CrO42- + 3 e- Cr3+
CrO42- + 3 e- Cr3+ + 4 H2O
8 H+ + CrO42- + 3 e- Cr3+ + 4 H2O

8 H+ + CrO42- + 3 e- Cr3+ + 4 H2O

Half equation :Changes in OS : +6 +3 ; reduction

Different
in
OS
=
3,
so
3
e
at the LHS of equation

Since there are 2 Cr , so total e- = 6 ; Cr2O72- + 6 e- 2 Cr3+

c) Cr2O72- Cr3+
Cr O 2- + 6 e- 2 Cr3+ + 7 H O

7
+

14 H + Cr2O72- + 6 e- 2 Cr3+ + 7 H2O

14 H+ + Cr2O72- + 6 e- 2 Cr3+ + 7 H2O

Changes in OS : +7 +2 ; reduction
d)MnO4- Mn2+

Different in OS = 5, so 5 e- at the LHS of equation

MnO4- + 5 e- Mn2+
MnO4- + 5 e- Mn2+ + 4 H2O
8 H+ + MnO4- + 5 e- Mn2+ + 4 H2O

+
2+
8
H
+
MnO
+
5
e

Mn
+ 4 H 2O
4
Half equation :
..
Changes in OS : +3 +5 ; oxidation
Different
in OS = 2, so 2 e- at the RHS of equation
e) NO2- NO
3 NO2 NO3 + 2 e
NO2- + H2O NO3- + 2 eNO2- + H2O 2 H+ + NO3- + 2 e-

+
NO
+
H
O

2
H
+
NO
+
2
e
2
2
3

in OS : +3 +6 ; oxidation
Half equation Changes
:
Different in OS = 3, so 3 e- at the RHS of equation
..
2CrO
2 CrO4 + 3 e
2f) CrO2 CrO4
2

2 H2O + CrO2 CrO4 + 3 e

2 H2O + CrO2- 4 H+ + CrO42- + 3 e-

2 H2O + CrO2- 4 H+ + CrO42- + 3 e-

g) As2O3 As2O5

Changes in OS : +3 +5 ; oxidation
Different in OS = 2, so 2 e- at the RHS of equation

Since there are 2 As , so total e = 4 ; As2O3 As2O5 + 4 e

As2O3 + 2 H2O As2O5 + 4 e
As2O3 + 2 H2O As2O5 + 4 e- + 4 H+
Half equation :

As2Oof3 +both
2 oxidation
H2O and
As2O
+ 4 H are
When half equation
reduction
5 + 4 e reaction
-

written, a redox reaction can be balanced.

Example 10 : Cu2+ (aq) + Na (s) Cu (s) + Na+ (aq)
Oxidation half equation :
.

X2
Na Na+ + eReduction half equation :

Cu2+ + 2 e- Cu
Overall equation :
..
2+
+
Cu
+
2
Na

Cu
+
2
Na
Example 11 :
Fe2+ (aq) + MnO4- (aq) Fe3+ (aq) + Mn2+ (aq)
Oxidation half equation :

Reduction half equation :

Fe2+ Fe3+ + e- X 5

8 H+ + MnO4- + 5 e- Mn2+ + 4 H2O

Overall equation :
..

5 Fe2+ 8 H+ + MnO4- Mn2+ + 4 H2O + 5 Fe3+

Example 12 :

ClO- (aq)

Oxidation half equation :

Reduction half equation :
Overall equation :

+ SO2 (g)

Cl- (aq) +

SO42-

....

2 H2O + SO2 4 H+ + SO42- + 2 e-

..

2 H+ + ClO- + 2 e- Cl- + H2O

H2O + ClO- + SO2 2 H+ + SO42- + ClExample 13 :

Cr2O72

Cl2

ClO3

Cr3+

Oxidation half equation :

..

Reduction half equation :

6 H2O + Cl2 12 H+ + 2 ClO3- + 10 e-

Overall equation :

X3

14 H+ + Cr2O72- + 6 e- 2 Cr3+ + 7 H2O X 5

5 Cr2O72- + 34 H+ + 3 Cl2 6 ClO3- + 17 H2O + 10 Cr3+

 Other than using half equation, a redox reaction can also be

balanced using the change of oxidation number.

Supposed we have a reaction : x A + y B products
If the oxidation of reactant A increased by m while B
reduced by n ;
Then x (+ m)
+
y ( n )
=
0
Using a simple reaction :
ySn4+ (aq)
+ xFe2+ (aq)
Sn2+ (aq)
+
Fe3+
(aq)
2
+4
+2
For Sn ; O.N changed from
to ; so the difference
+ 1 is
+2 +3
..
For Fe ; O.N changed from to ... ; so the difference is
x (+ 1) + y ( 2) = 0
..
So, x = 2 ; y = 1
This 1will
makes
Sn4+
(aq) the
+ 2 equation
Fe2+ (aq) become
Sn2+ : (aq) + Fe3+ (aq)

Sn4+ (aq) + 2 Fe2+ (aq)

Sn2+ (aq) + 2 Fe3+ (aq)

Balanced the number of atoms on both side of the equation

Example 14 : Br (aq) + SO42- (aq)

SO2 (g) +
+1
-1
0
Br2 (l)
For Br ; O.N changed from
+6
+4 to . ; so the - 2
difference is
For S ; O.N changed from to . ; so the
x (+ 1) + y ( 2) = 0
difference is
So, x = 2 ; y = 1
This will make
equation
22 Br (aq) +the
1 SO
(aq) become
Br (l) +: SO (aq)
4

2 Br (aq) + SO42- (aq) + 4 H+ Br2 (l) + SO2 (aq) + 2 H2O

Balanced the number of atoms on both side of the

equation
2Example
15 changed
: CrO4from
+
Cr3+ is+3 Cl2
For Cr ; O.N
+6 toCl
+3- ; so
the difference
For Cl ; O.N changed from 1 to 0 ; so the difference is +1
x (+ 1) + y ( 3) = 0

So, x = 3 ; y = 1

8 H+ + CrO42- + 3 Cl- Cr3+ + 3/2 Cl2 + 4 H2O

16 H+ + 2 CrO42- + 6 Cl- 2 Cr3+ + 3 Cl2 + 8 H2O

3+ +
Example
16 changed
: Cr2O72-from
+ +6NO
Crdifference
NO
3
For Cr ; O.N
to2-+3 ;
so the
is 3
Since there are 2 Cr involved, diff. = 6
For N ; O.N changed from +3 to +5 ; so the difference is +2

x (+ 2) + y ( 6) = 0

So, x = 3 ; y = 1
23+
Cr
O
+
3
NO

Cr
+
NO
2
7
2
3

+
23+
8 H + Cr2O7

+ 3 NO2

2 Cr

+ 3 NO3 + 4 H2O

 If the redox reaction occur in a basic solution, the

number of H+ shall be neutralise by the number of

OH-.
Example
: MnO
SO332-2-
+ 42-SO
Oxidation17
eq
: H42-O ++ SO
2 MnO
H+ +2 SO
+ 422-e- X 3

Reduction eq : 4 H+ + MnO4- + 3 e- MnO2 + 2 H2O X 2

+
22Overall
:
2
H
+
2
MnO
+
3
SO

2
MnO
+
3
SO
+ H2O
4
3
2
4

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

2
Example
18eq: : Fe(OH)
+ CrO
+ eFe(OH)

4
Oxidation
H2O + 2Fe(OH)

Fe(OH)
+ H+ 3 +
2
3
X3
Cr(OH)3
Reduction eq : 5 H+ + 3 e + CrO42 Cr(OH)3 + H2O
Overall : 2 H2O + 3 Fe(OH)2 + 2 H+ + CrO42 3 Fe(OH)3 + Cr(OH)3
In basic : 4 H2O + 3Fe(OH)2 + CrO42 3Fe(OH)3 + Cr(OH)3 + 2OH

Disproportionation reactions
~ Substances which are able to undergo self oxidation
reduction are called disproportionation
~ Examples of disproportionation reaction.
18. Cu+ (aq)
+ Cu+ (aq) Cu2+ (aq) + Cu
(s) +1
+2
0

0 Cl2 (aq) -1 NaCl (aq)

+1 + NaOCl
19. NaOH (aq) +
(aq) + H2O

20.

+5
+1
NaOBr (aq) NaBrO3 (aq)

-1
+NaBr (aq)

2.3 Electrode Potential

When a strip of metal, M (s) (known as electrode)
is placed in a solution of its aqueous solution, M n+
(aq), the following equilibrium is established : Mn+
(aq) + n e- M (s)
At equilibrium, there is a separation of charge
between metal (M) and ions (Mn+) in the solution. as
a result, there is a potential difference between
the metal and the solution. This potential
difference is known as electrode potential and
is written as Eo.
Electrode potential can be measure under these
circumstances where

Metal

M
M+

M+
M+

M+

M+

M+

Cu2+ + 2e- Cu E Cu / Cu 0.34 V

The positive value of E0 indicates the equilibrium favours to
2

right position. Copper (II) ions (Cu2+), have a greater

the
be reduced at copper electrode.
tendency to ...
Zn2+ + 2e- Zn E Zn / Zn 0.76 V
The negative value of E0 indicates the equilibrium favours to
left position. Zinc ion (Zn2+) have a greater tendency to
the ..
be oxidised at zinc electrode.
..
2

Non Metal
Cl2 (g)

Cl- (aq) [1.0 M]

F2 + 2e- 2 F-

EF

Cl2 + 2e- 2 Cl-

E Cl

/ F

/ Cl

2.87 V

1.36 V

Positive value of ECl2/Cl- and EF2/F- indicates the equilibrium

Fluorine and chlorine

right
favours to the.
position. has a
be reduced
greater tendency to under platinum electrode
The more positive the value, higher the tendency of nonbe reduced
metal to .
oxidising
In another words, fluorine is a stronger .. agent than

Mixture of aqueous ion

Ma+ [1.0 M] / Mb+ [1.0 M]

A potential difference also exists between ions in an aqueous

solution. Example :
Cr3+ + e- Cr2+
Fe

3+

+ e Fe
-

2+

E Cr 3 / Cr 2 0.41 V
E Fe3 / Fe 2 0.77 V

more
Base on the Eo value, Cr3+ is
stable than Cr2+ as
backward
equilibrium favour to .. (Eo is negative)
less stable than Fe2+ as
Base on the Eo value, Fe3+ is ..
forward (Eo is positive)
equilibrium favour to ..

2.3.1 Standard Electrode Potential

Definition : The standard electrode potential, Eo Mn+ /

of a metal M
is the potential
difference between the metal M and the aqueous

-3
mol dm at 298
solution of the metal ions of concentration1.0

K
Hydrogen Electrode
and 1.0
. atm, measured relatively to Standard
.
M

Standard Hydrogen Electrode ( S.H.E.)

It is impossible to measure the electrode potential for an

incomplete half-cell. It can only be measured for a complete

..
cell , i.e. only differences in electrode potentials
circuit with 2 half
.
are measurable.
The standard chosen for electrode potentials is the standard
hydrogen electrode (SHE). The standard electrode potentials of
other half-cells are measured relative to the SHEs electrode
potential.
By convention, the standard electrode potential for this
reference hydrogen half-cell is taken to be standard
...

2 H+ (aq) + 2 eH2 (g)

25 oC ; H (g) at
1.0atm
Condition : ....
2

; [H+] = 1.00 M

Measuring standard electrode potential of a

metal / metal aqueous solution
The set-up of the apparatus to measure the
standard potential electrode, Eo. is
Potentiometer
described as below
:
0.76 V

H2 (g)
1.0 atm
Salt
bridge
H+ (aq) [1.0 M]
(made of
o
25 C
saturate
d KCl /
Standard hydrogen electrode
NaCl)

Zn (s)

Zn2+ (aq)
[1.0 M]
Zinc half cell

 The chemical cell is set-up by connecting a standard

+
2+
H
/H2 electrode.
Zn
/Zn
.. half-cell to a standard .
0.76 V. The potentiometer point to
The e.m.f. for the cell is .
2
the direction of ..Helectrode
in the
external circuit,
2+
+
Zn
/
Zn
H
/H
indicating electrons flow from .. to .2 half-cell.
Eq. Zn half-cell :
Zn (s) Zn2+ (aq) + 2 e Eq. H half-cell
:
+
2
H
(aq) + 2 e- H2 (g)
Overall reaction :
+
2+
Zn
(s)
+
2
H
(aq)

H
(g)
+
Zn
(aq)
2
The cell notation can be written as :

Zn (s) I Zn2+ (aq) II H+ (aq) , H2 (g) I Pt (s)

At zinc electrode ; electrons are .....
donated; ...
oxidation
reaction occur
At platinum electrode ; electrons are ..
received; .
reduction
reaction occur
Since zinc is oxidised in a SHE, the standard e.m.f value is
0.76 V

 Another example : silver / silver aqueous solution (Ag /

Ag+)
The set-up of the apparatus to measure the standard
o. is described as below :
potential electrode, EPotentiometer
0.80 V

H2 (g)
1.0 atm

H (aq) [1.0 M]
25oC
+

Ag (s)
Salt
bridge
(made of
saturate
d KCl /
NaCl)

Standard hydrogen electrode

Ag+ (aq)
[1.0 M]

Silver half cell

 The chemical cell set-up by connecting a standard

H+ / H2
Ag+ / Ag

half-cell to a standard ..
electrode.
The e.m.f. for the cell is 0.80
. V. The galvanometer point to
silver
the direction of ..
electrode in the external circuit,
+
+
H
/
H
Ag
/ Ag half-cell.
2
indicating electrons flow from .. to
Ag half-cell :
Ag+ (aq) + e- Ag (s)
H2 half-cell :
H2 (g) 2 H+ (aq) + 2 e Overall : H (g) + 2 Ag+ (aq) 2 Ag (s) + 2 H+ (aq)
2
The cell notation can be written as :
Pt (s) I H2 (g) , H+ (aq) II Ag+ (aq) I Ag (s)
received ;
reduction
At silver electrode ; electrons are .
reaction occur
oxidation
donated ;
At platinum electrode ; electrons are
reaction occur
Since silver is reduced in a SHE, the standard value is
+ 0.80 V

Measuring a standard electrode potential of

a gaseous
substance
Cl2 / Cl
The chemical cell set-up by connecting a standard
H+ / H2
half-cell to a standard
electrode. Note that the
set-up of the half-cells are the same for gaseous substances
Potentiometer
1.36 V

H2 (g)
1.0 atm
Salt
bridge
H+ (aq) [1.0 M]
(made of
25oC
saturate
d KCl /
NaCl)
Standard hydrogen electrode
Chlorine half cell

Cl2 (g)
1 atm

Cl- (aq)
[1.0 M]

 The e.m.f. for the cell is 1.36

.V. The galvanometer point to

Pt (Cl2) electrode in the external circuit,

the direction of ..
H+ / H2 to .
Cl2 / Cl halfindicating electrons flow from ..
cell.
Chlorine half-cell : Cl2 (g) + 2 e- 2 Cl (aq)
Hydrogen half-cell : H (g) 2 H+ (aq) + 2 e2
Overall : : H (g) + Cl (g) 2 Cl (aq) + 2 H+ (aq)
2
2
The cell notation can be written as :

Pt (s) I H2 (g) , H+ (aq) II Cl2 (g), Cl (aq) I Pt (s)

At platinum electrode in the half-cell of hydrogen ; electrons
are donated
;
oxidationreaction occur
At platinum electrode in the half-cell of chlorine ; electrons
are ..
received ;
reduction reaction occur
Since chlorine is
reduced by SHE, the standard value is
+ 1.36 V
.

Measuring a standard electrode potential of a mixture of metal

ions.
The electrode potential of a mixture of ions can be measured
in the similar way, using standard hydrogen electrode (SHE)
as the other half-cell of the chemical cell
For example, in a mixture of iron (II) and iron (III) ion
Potentiometer

0.77 V

H2 (g)
1.0 atm
H+ (aq) [1.0 M]
25oC

Salt
bridge
(made of
saturate
d KCl /
NaCl)

Standard hydrogen electrode

Fe2+ (aq)
Fe3+ (aq)
[1.0 M]
Fe2+ / Fe3+ half

Fe3+ / Fe2+
The chemical cell set-up by connecting a standard
H+ / H2
half-cell to a standard
electrode. Note that the set-

up of the half-cells are a mixture of iron (II) and iron (III) ion
platinum as electrode.
under standard condition with
0.77 V. The galvanometer point to the
The e.m.f. for the cell is .
Fe3+ / Fe2+ half cell in the external circuit, indicating
direction of ...
3+
/ Fe2+ half-cell.
H+ / H2
electrons flow from .
to Fe
.
Fe3+ / Fe2+ half-cell :
Fe3+ (aq) + e- Fe2+ (aq)
Hydrogen half-cell :
H2 (g) 2 H+ (aq) + 2 e Overall reaction :H (g) + 2 Fe3+(aq) 2 Fe2+ (aq) + 2 H+ (aq)
2
The cell notation can be written as :
Pt (s) I H2 (g) , H+(aq) II Fe3+(aq), Fe2+(aq) I Pt (s)
At half-cell of hydrogen ; electrons are donated
; oxidation

reaction occur
At half-cell of Fe3+/Fe2+ ; electrons are .
received ; ...
reduction

reaction occur
Since the mixture is ...
+ 0.77 V
reduced by SHE, the value of

The calomel electrode

primary
Platinum electrode is known as
the
reference electrode. However, it is relatively difficult
to set up and operate under standard condition. It is
base alloy
more easier secondary
and safer to use a calomelMercury
electrode
as
a electrode. [calomel =
..]. Diagram of a typical calomel
electrode

2.4 Factors Affecting Electrode Potential

By convention, the half equation is writtenreduction
with .
as the forward reaction.
The magnitude of the electrode potential depends on the
position of the above equilibrium
When value is positive ;forward
a reaction is
favoured
backward
When value is negative ; a .. reaction is
favoured
Factors which affect the position of equilibrium would
therefore affect the value of electrode potential
electropositive
1. Nature of metal
electron
When a metal is highly .., the metal
atoms have a greater tendency to become positive ions,
negative behind on the metal electrode. The
leaving the
leftpotential
oxidation
electrode
therefore become more .
and the position of equilibrium shift more to
(. is favoured)

Metal

Half equation

E (V)

Silver

Ag+ + e- Ag

+ 0.80

Lead

Pb2+ + 2 e- Pb

0.13

Zinc

Zn2+ + 2 e- Zn

0.76

Magnesium

Mg2+ + 2 e- Mg

2.38

2. Concentration of metal
If the concentration of the hydrated metal ions is increased in the
right
equilibrium, the position of equilibrium will shift to the ,
positive
forward ; electrode potential become more
favouring .
Pb2+ (aq) + 2 ePb (s) E = 0.13 V [ Conc = 1.0 M ]
If concentration Pb2+ changed to 0.001 M ; equilibrium shift to
backward ; E < 0.13 V
.
If concentration Pb2+ changed to 10.0 M ; equilibrium shift to
forward
.
; E > 0.13 V

3 Temperature
Most of the reduction processes are exothermic
process. Increasing the temperature will cause the
endothermic
equilibrium to shift to the
position of ..
left ; which is to the Thus, the electrode
process
negative / less positive
potential becomes more .
4.
Pressure for gaseous species
From what weve learned from chemical equilibria,
when pressure increased, equilibrium will shift to the
less
position with .. mole of gas ; while decreasing
more
pressure will cause equilibrium to shift to position with
.mole of gas.
Eg : Cl2 (g) + 2 e2 Cl- (aq)
E = + 1.36 V
Increasing
will cause equilibrium shift to
right side pressure
>

.. ; E
+ 1.36 V
Decreasing
left side
pressure
will cause equilibrium shift to
<
.. ; E
+ 1.36 V

2.5 The electrochemical series (ECS)

When a series of standard reduction potential of different
substances are determined and are arranged in order, a
electrochemical series is obtained.

Below are some important facts about electrochemical series.

Half cell of the standard electrode potential is always written
as reduction
processes. Due to this reason, sometimes it is
Standard reduction potential (SRP)
also known as
The positive / negative sign shows how substances favour to
each of the reaction.
forward reaction.
If the EO is positive, substances favour a ..
oxidising agent. The
In another words, it serve well as .
oxidising agent
more positive the value ; the stronger the ..
If the EO is negative, substances favour backward
.. reaction.
In another words, it serve well as
reducing agent. The
reducing agent
more negative the value ; the stronger the
The number of electron involve does not affect the standard
electrode potential value. If
Cl2 (g) + 2 e- 2 Cl- (aq) Eo = + 1.36 V ; then
1.36 V
Cl (g) + e- Cl- (aq) Eo = +
.
2

 Some substances have more than one Eo value. For example

Fe2+ ; H2O2 ; NO2- ; Cu+. These substances can act as an

oxidising or reducing agent. Examples
In Fe2+
Fe3+ (aq) + e- Fe2+ (aq)

(Fe2+ act as reducing agent)

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

(Fe2+ act as oxidising agent)

2.6 Redox reaction and electromotive forces (e.m.f.)

In standard hydrogen electrode, we had seen on how to
measure the standard electrode potential of 3 types of halfcell, which are metal / metal ion half-cell ; non-metal / ion halfcell ; ion / ion half-cell
Imagine if we replace the hydrogen half-cell with other halfcell, will we still get the same value?
The potential difference between 2 half-cells can be
measured using the same way. There are various types of the
set-up of a complete chemical cell other than the one
introduced during measuring the standard electrode potential,
such as Daniel cell (diagram below)

 A Daniel cell is built using a copper and

V
C
u

Z
n

Cu2+

Zn2+

zinc half-cell
complete the cell
A porous pot is used to
And to separate between the 2 electrolytes

Substance which has a higher position in

anode
ECS
(more negative the value of Eo) is the
of the cell whereas the substance
cathode
which has a lower position in ECS (more
positive the value of Eo) is the
of the cell.
Zn Zn2+ + 2 e- Eo =+0.76 V
The half equation occur at
Cu2+ + 2 e- Cu Eo = +0.34 V
Anode :
Zn + Cu2+ Zn2+ + Cu Ecell =+1.10 V
Cathode :
+ 1.10
Overall :

e.m.f.
Zn (s) IThe
Zn2+
(aq) ofII cell
Cuis2+.
(aq) I CuV (s)
Cell notation is written as

A U tube cell is built using iron (II) ion,

Fe2+ and bromine water, Br2
H2SO4 is used tocomplete the cell
Br2/Br Fe3+/Fe2+ .
And to separate between the 2 electrolytes
..............
.
G
anode
The substance which has more
negative / less positive the value of E o)
is the of the cell whereas the
cathode which has a more positive /
substance
less negative value of Eo is the
... of the cell.
Pt
Fe2+ Fe3+ + e- Eo = - 0.77 V
The half equation occur at
o
Br
+
2
e

2
Br
E
= +1.07 V
2
Anode
:
2+
3+
CathodeBr2:+ 2 Fe 2 Fe + 2 Br
+ 0.30
Overall :
The e.m.f. of cell is .. V
3+
Pt (s) I Fe2+ (aq)Cell
, Fenotation
(aq) II isBrwritten
as (aq) I Pt (s)
2 (l) , Br-

Note the following in a chemical cell :

POSITIVE In another words,
The e.m.f. of a cell is always
more positive standard
we must always subtract the ..
less positive standard electrode
electrode potential with a .
potential.
anode tocathode
Electrons flow from
in the external
circuit
Oxidation reaction occur at anode while
reduction reaction

occur at cathode of the cell.

Fe / Fe2+ half cell

SRP for both cell :

Mg / Mg2+ half cell

Fe2+ + 2e- Fe

Mg2+ + 2e- Mg

E0 = - 0.44 V

E0 = - 2.38 V

Since E0 for Mg2+/Mg is more negative than Fe2+/Fe, so Mg2+/Mg

will be oxidised, so SPR of Mg2+/Mg is reversed
Oxidation eq : Mg Mg2+ + 2 e-

E0 = + 2.38 V

Reduction eq : Fe2+ + 2e- Fe

E0 = 0.44 V

Overall eq : Fe2+ + Mg Fe + Mg2+ Ecell = + 1.94 V

Cell diagram : Mg (s) I Mg2+ (aq) II Fe2+ (aq) I Fe (s)

MnO4- / Mn2+ half cell

Ti3+ / Ti2+ half cell

SRP : MnO4- + 5 e- + 8 H+ Mn2+ + 4 H2O E0 = + 1.52 V

Ti3+ + e- Ti2+

E0 = 0.37 V

Since E0 for Ti3+/Ti2+ is more negative than MnO4-/Mn2+, so Ti3+/Ti2+

will be oxidised, so SPR of Ti3+/Ti2+ is reversed
Oxidation eq : Ti2+ Ti3+ + e-

E0 = + 0.37 V

Red eq : MnO4- + 5 e- + 8 H+ Mn2+ + 4 H2O E0 = + 1.52 V

Overall: MnO4- + 5 Ti2+ + 8 H+ Mn2+ + 4 H2O + 5 Ti3+ Ecell = + 1.89V
Cell diagram: Pt(s) I Ti2+(aq), Ti3+ (aq)II MnO4- (aq), Mn2+(aq) I Pt(s)

2.7 Feasibility of a redox reaction

If a reaction occurs on its own record when the
spontaneous
reactants are mixed,
the reaction is a ...
reaction
Compare the following reaction to distinguish
Immerse
a zinc a
plate
into HCl 1.0 M reaction
Immerse and
a copper
plate
into HCl 1.0 M
between
spontaneous
not
spontaneous
reaction.

Observation

-Bubbling is observed
-Zinc plate is corroded by HCl

Observation

- No changes occur

 We can use e.m.f. to predict the feasibility of the reaction.

Supposedly, in the reaction above, the 2 half equation for

the reactions can be written as
-Since Zn react with H+, so the 2 half
equation can be written
Zn Zn2+ + 2eE0 = + 0.76 V
2 H+ + 2e- H2
E0 = + 0.00 V
Zn + 2 H+ Zn2+ + H2 E = + 0.76 V
Since Ecell is positive, the reaction is
spontaneous

-Since Cu react with H+, so the 2 half

equation can be written
Cu Cu2+ + 2eE0 = - 0.34 V
2 H+ + 2e- H2
E0 = + 0.00 V
Cu + 2 H+ Cu2+ + H2 E = - 0.34 V
Since Ecell is negative, the reaction is
nonspontaneous

It can also be used to deduce the strength as an oxidising

Cl2 (aq) + e- Cl (aq) Eo = + 1.36 V

Br2 (aq) + e- Br (aq) Eo = + 1.07 V

Stronger
oxidising agent

agent in halogen.
Halogens are strong oxidising agent. This is supported with
the value of standard reduction potential where
F2 (aq) + e- F (aq) Eo = + 2.87 V

Observation
Chlorine in
Tetrachlorometha Pale yellow solution in
ne is added to
CCl4 turned brown when
aqueous
shaken with KBr.
potassium
bromide (KBr).
Bromine in
tetrachlorometha
ne is added to
aqueous
potassium iodide
(KI)
Iodine is
tetrachlorometha
ne is added to
aqueous
potassium
chloride (KCl)

Brown solution in CCl4

turned purple when
shaken with KI

Half equation & overall

equation
Cl2 + 2e- 2Cl-

Eo = + 1.36 V

2Br- Br2 + 2e-

Eo = - 1.07 V

Cl2 + 2Br- Br2 + 2Cl

Ecell = + 0.29 V

Br2 + 2e- 2Br-

Eo = + 1.07 V

2I- I2 + 2e-

Eo = - 0.54 V

Br2 + 2I- I2 + 2Br

Ecell = + 0.53 V
I2 + 2e- 2I-

Eo = + 0.54 V

No changes occur. Purple

2Cl- CI2 + 2e- Eo = - 1.36 V
solution remain after
I2 + 2 Cl- Cl2 + 2 I
shaken with KCl
Ecell = - 0.82 V

a) Iron nail are placed in zinc sulphate

Reactant : Fe and Zn2+

Suitable half equation
Fe Fe2+ + 2eEo = + 0.44 V
Zn2+ + 2e- Zn Eo = - 0.76 V
Fe + Zn2+ Fe2+ + Zn Ecell = - 0.32V
Since Ecell is negative, reaction is not
spontaneous (cannot react)
c) Chlorine gas is bubbled into acidified
potassium dichromate

Reactant : Cl2 and Cr2O72

Suitable half equation
Cl2 + 2H2O 2HOCl + 2H+ + 2e
Eo = 1.64 V
Cr2O72- + 6e- + 14H+ 2Cr3+ + 7H2O
Eo = + 1.33 V Cr2O72- +
6HOCl + 2H+ 3Cl2 + H2O
Ecell = 0.31V
Since Ecell is negative, reaction is non

b) Copper is placed in concentrated nitric

acid solution (Assume NO2 (g) is produced)

Reactant : Cu and NO3Suitable half equation

Cu Cu2+ + 2eEo = - 0.34 V
NO3 + 2H+ +e NO2 + H2O E0= +0.81 V
Cu + 2 NO3 + 4H+ 2NO2 +2H2O + Cu2+
Ecell = + 0.47 V

Since Ecell is positive, reaction is

spontaneous (can react)

d) potassium iodide is added to acidified

potassium manganate (VII) solution

Reactant : I- and MnO4Suitable half equation

2I- I2 + 2 eEo = - 0.54 V
MnO4- + 8 H+ + 5e- Mn2+ + 4 H2O
Eo = + 1.52 V
10 I- + 2 MnO4- + 16H+ 2 Mn2+ + 8 H2O
+ 5 I2
Ecell = + 0.98 V

Since Ecell is positive, reaction is

spontaneous (can react)

e) Calcium metal is added to water

Reactant : Ca and H2O

Suitable half equation
2H2O + 2e- H2 + 2OH- Eo = - 0.83 V
Ca Ca2+ + 2eEo = + 2.87 V
Ca + 2H2O H2 + Ca2+ + 2 OHEcell = + 2.04 V
Since Ecell is positive, reaction is
spontaneous (can react)

f) Acidified potassium dichromate solution

is added to a solution of iron (II) sulphate

Reactant : Fe2+ and Cr2O72Suitable half equation

Cr2O72- + 6e- + 14H+ 2Cr3+ + 7H2O
Eo = + 1.33 V
Fe2+ Fe3+ + eEo = - 0.77 V
Cr2O72- + 6Fe2+ + 14H+
2Cr3+ + 7H2O + 6Fe3+
Ecell = + 0.56 V
Since Ecell is positive, reaction is
spontaneous (can react)

 Among the oxidation states available in d-orbital, +2 and +3

oxidation states are the most common states available in the dblock elements.
The stability of the oxidation state can be explained in terms of

electrochemistry. The standard reduction potential of a few

transition metals is given in the table below.

Half equation of
reduction
Cr3+ + e- Cr2+

Eo (V)

Stable ion

0.41

Cr3+

Ti3+ + e- Ti2+

0.37

Ti3+

V3+ + e- V2+

0.26

V3+

Fe3+ + e- Fe2+

+ 0.77

Fe2+

Mn3+ + e- Mn2+

+ 1.51

Mn2+

Co3+ + e- Co2+

+ 1.82

Co2+

 The action of dilute acids on metal are usually carried out in

the presence of oxygen. We must therefore determine

whether oxygen has any effect on such reactions. For
example, in oxidation of iron (II) ion
Action of acids on iron (II) ion in the

Action of acids on iron (II) ion in the

absence of air (oxygen)

presence of air

Fe2+ Fe3+ + eE0 = - 0.77 V

2 H + + 2 e- H 2
E0 = + 0.00 V
2 Fe2+ + 2H+ 2 Fe3+ + H2
Ecell = - 0.77 V

Fe2+ Fe3+ + eE0 = - 0.77 V

O2 + 4H+ + 4e 2H2O E0 = +1.23 V
4Fe2+ + O2 + 4H+ 4Fe3+ + 2H2O
Ecell = + 0.46 V

..
and
can also react in the same
2+
2+
2+

Ti
V
Cr
way as iron does.
For the case of cobalt and manganese, it does not react in
the same way as iron does. Consider the reaction of cobalt
(II) ion with acid in the absence / presence of oxygen

Action of acids on cobalt in the absence of air

Co2+ Co3+ + eE0 = - 1.82 V

2 H + + 2 e - H2
E0 = + 0.00 V
2 Co2+ + 2H+ 2 Co3+ + H2
Ecell = - 1.82 V

Action of acids on cobalt in the presence of air

Co2+ Co3+ + eE0 = - 1.82 V

O2 + 4H+ + 4e 2H2O E0 = +1.23 V
4Co2+ + O2 + 4H+ 4Co3+ + 2H2O
Ecell = - 0.59 V

Graph below shows the relative stability of ions which exist in different oxidation
state

 Other than the presence of oxygen, the presence of ligands can

also affect the stability of ions.

Consider the following electrode reactions for cobalt :

[Co(NH3)6]3+ + e- [Co(NH3)6]2+ E0 = + 0.10 V

O2 + 4 H+ + 4 e- 2 H2O
[Co(H2O)6]3+ + e-

E0 = + 1.23 V

[Co(H2O)6]2+

E0 = + 1.82 V

In water, Co2+ is stable toward oxidation, even in the presence of

oxygen, since the E for the reaction is -0.59 (based on the

calculation above). Therefore, +2 is more stable than +3 oxidation
state in aqueous solution (ligand is water)
When aqueous NH3 is added to the solution of Co2+, the complex

ion [Co(NH3)6]2+ is formed (since NH3 is a strong ligand, water

molecule can easily displaced by NH3 ligand).

Eq : [Co(H2O)6]2+ + 6 NH3 [Co(NH3)6]2+ + 6 H2O

When [Co(NH3)6]2+ is formed, it can react easily with acids with the

presence of air

 When [Co(NH3)6]2+ is formed, it can react easily with acids

with the presence of air

[Co(NH3)6]2+ [Co(NH3)6]3+ + eO2 + 4 H+ + 4 e- 2 H2O

E0 = - 0.10 V
E0 = + 1.23 V

4 [Co(NH3)6]2+ + O2 + 4 H+ 2 H2O + 4 [Co(NH3)6]3+

Ecell = + 1.13 V
Therefore, although Co3+ is not stable in the presence of air,

but Co3+ is stable in ammonia aqueous solution. Hence, this is

one of the ways to prepare an ion solution which is not stable
in air.

2.7 Nernst Equation and Its application

All the electrochemical cells that discussed so far are
25 oC ;
1.00 atm
1.00
standard Eo. [At ..
; . M]
If concentration of ions and temperature change, it will affec
the value of electrode potential. At this moment, we can use
an equation to study the changes of concentration of ions
using Nernst Equation.
E E0

[reac tan t ions] x

RT

ln
nF
[product ions] y

R = 8.31 J mol-1 K-1

T = 250C = 298 K
F (Faraday constant)
F = 96500 C mol-1

x
(
8
.
31
)(
298
)(
2
.
303
)
[
reac
tan
t
ions
]
E E0
lg
n (96500)
[product ions]y

x
0
.
059
[
reac
tan
t
ions
]
E E0
lg
n
[product ions]y

Ag / Ag+ (1.5 mol dm-3)

Ag+ + e- Ag E0 = + 0.80 V

Cu / Cu2+ (2.0 mol dm-3)

Cu2+ + 2e- Cu E0 = + 0.34 V

1
0
.
059
[
Ag
]
E E0
lg
n
1
0.059 (1.5)1
E 0.80
lg
1
1

2 1
0
.
059
[
Cu
]
E E0
lg
n
1
0.059 (2.0)1
E 0.34
lg
2
1

E = + 0.81 V

E = + 0.35 V

Cl2 / Cl- (0.50 mol dm-3)

Cl2 + 2e- 2 Cl- E0 = + 1.36 V

1
0
.
059
[
Cl
]
E E0
lg 2 2
n
[Cl ]

0.059
(1)1
E 1.36
lg
2
(0.50) 2
E = + 1.38 V

Fe3+ (0.800 mol dm-3) / Fe2+ (1.30 mol dm3

)

Fe3+ + e- Fe2+ E0 = + 0.77 V

0.059 [Fe3 ]1
E E
lg
n
[Fe 2 ]1
0

0.059 (0.800)1
E 0.77
lg
1
(1.30)
E = + 0.758 V

Ti3+ (1.20 mol dm-3) / Ti2+ (0.700 mol

dm-3)
Ti3+ + e- Ti2+ E0 = - 0.37 V
3 1
0
.
059
[
Ti
]
E E0
lg 2 1
n
[Ti ]

E 0.37

0.059
(1.20)
lg
1
(0.700)

E = - 0.356 V

MnO4- (1.10 mol dm-3) ; H+ (0.800 mol

dm-3) / Mn2+ (17.0 mol dm-3)
MnO4- + 8 H+ + 5e- 4 H2O + Mn2+
E0 = + 1.52 V

8
0
.
059
[
MnO
][
H
]
4
E E0
lg
n
[Mn 2 ]

0.059 (1.10)(0.800)8
E 1.52
lg
5
(17.0)
E = + 1.50 V

13.7.1 Nernst Equation and e.m.f. of a chemical cell.

Consider the following redox reaction in an chemical cell
p A + q B r C + s D
At 25oC, Nernst Equation :
E E0

[reac tan t ions] x

RT

ln
nF
[product ions] y

E E cell

0.059 [A]p [B]q

lg
n
[C]r [D]s

*For pure solids and liquids, it will not appear in the

equation

a) Cr (s) Cr3+ (0.010 mol dm-3) Ni2+ (0.20 mol dm-3) Ni (s)

Oxidation
: Cr Cr3+ + 3 e E0 = + 0.74 V
Reduction
: Ni2+ + 2 e Ni
E0 = 0.25 V
Overall : 2 Cr + 3 Ni2+ 3 Ni + 2 Cr3+ Ecell = + 0.49 V
E E cell

0.059
[ Ni 2 ]3

lg
6
[Cr 3 ]2

0.059
(0.20) 3
E 0.49
lg
6
(0.010) 2

E = + 0.51 V

b) Mg (s) Mg2+ (0.500 mol dm-3) Fe3+ (1.80 mol dm-3) , Fe2+

(0.750 mol dm-3) Pt (s)

Oxidation
: Mg Mg2+ + 2e
E0 = + 2.38 V
Reduction
: Fe3+ + e- Fe2+
E0 = + 0.77 V
Overall : Mg + 2 Fe3+ Mg2+ + 2 Fe2+
Ecell = + 3.15 V
E E cell

0.059
[ Fe3 ]2

lg
2
[Mg 2 ][Fe 2 ]2

0.059
(1.80) 2
E 3.15
lg
2
(0.500)(0.750) 2

E = + 3.18 V

c) Pt (s) Sn2+ (0.300 mol dm-3), Sn4+ (0.500 mol dm-3)

Mn3+ (1.20 mol dm-3) , Mn2+ (0.250 mol dm-3) Pt (s)
Oxidation
: Sn2+ Sn4+ + 2e
E0 = 0.15 V
Reduction
: Mn3+ + e- Mn2+
E0 = + 1.49 V
Overall : Sn2+ + 2 Mn3+ Sn4+ + 2 Mn2+ Ecell = + 1.34 V

E Ecell

3 2

0.059 [ Sn ][ Mn ]

lg
4
2 2
2
[ Sn ][ Mn ]

0.059
(0.300)(1.20) 2
E 1.34
lg
2
(0.500)(0.250) 2
E = + 1.37 V

2.7.1 Nernst Equation and Equilibrium Constant, KC

Consider the following reaction :

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

E0 = + 1.10 V

The Kc of the reaction can be expressed as

[ Zn 2 ]
Kc
[Cu 2 ]

decrease while
As time past, the concentration of [Cu2+]
increase
[Zn2+] ..

Using standard reduction potential of copper and zinc

Cu2+ (aq) + 2 e- Cu (s)

Eo = + 0.34 V ; when [Cu2+]

decrease ; equilibrium shift to
decrease
left Eo

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

Eo = 0.76 V ; when [Zn2+]

increase
increase
right Eo ...

; equilibrium shift to

V
+ 0.34

Half cell of Cu

0
Time / s

Half cell of Zn
0.76

 Applied to Nernst equation where

E E

[reac tan t ions] x

RT

ln
nF
[product ions] y

When system achieved equilibrium at room temperature,

Nernst equation is simplified to :

y
0
.
059
[
product
ion
]
E E0
lg
n
[ reactat ion ]x

Since

[ Zn 2 ]
Kc and2at
equilibrium, Ecell = 0, so
[Cu ]

0.059
0 V E
lg K C
n
0

Consider the following reaction :

2 Fe3+ (aq) + Cu 2 Fe2+ (aq) + Cu2+ (aq)
a) Calculate the E0 of the cell
b) Calculate the Kc for the reaction.

Fe3+ + e- Fe2+
E0 = + 0.77 V
Cu 2 e- + Cu2+
E0 = - 0.34 V
2 Fe3+ + Cu Cu2+ + 2 Fe2+
Ecell = + 0.43 V

KC

2 2

[Fe ] [Cu ]
[Fe3 ]2

Consider the following reaction :

Fe3+ (aq) + Ag (s) Fe2+ (aq) + Ag+ (aq)
a) Calculate the E0 of the cell
b) Calculate the Kc for the reaction.

Fe3+ + e- Fe2+
E0 = + 0.77 V
Ag e- + Ag+
E0 = 0.80 V
Fe3+ + Ag Fe2+ + Ag+
Ecell = 0.03 V

[Ag ][Fe 2 ]
KC
[Fe3 ]

0.059
0 V E
lg K C
2

0 V 0.03

0.059
lg K C
1

0.059
0 V 0.43
lg K C
2

0 V 0.03

0.059
lg K C
1

lg KC = 14.57
KC = 3.77 x 1014 mol dm-3

lg KC = 0.5085
KC = 0.310 mol dm-3

2.7.2

Nernst Equation and solubility product, Ksp

Similar to calculating equilibrium constant, solubility product of a

sparingly soluble salt can also be calculated in the same way

mentioned above. Consider the following reaction of dissociation of
AgCl (s)
AgCl (s) Ag+ (aq) + Cl- (aq)
Half-cell : AgCl (s) + e- Ag (s) + Cl- (aq)
Eo = + 0.22 V
Half-cell : Ag (s) Ag+ (aq) + e
Eo = - 0.80 V
Overall Eq: AgCl (s) Ag+ (aq) + Cl- (aq)
E0 = - 0.58 V

Using Nernst equation

and given Ksp = [Ag+][Cl]

y
0
.
059
[
product
ion
]
E E0
lg
n
[reactat ion ]x

0.059 [Ag ][Cl ]

EE
lg
n
1
0

0.059
EE
lg K sp
n
0

 At equilibrium ; E = 0 ; so replace in the equation

0 0.58 V

0.059
lg K sp
1

lg Ksp = 9.83 mol2 dm-6

Ksp = 1.48 x 1010 mol2 dm-6
The question may be extend to calculate the solubility

from the solubility product calculated

Note that Eo is always negative for sparingly soluble salt
very small
as Ksp is

 Example : Given HgCl2 + 2 e-

and Hg2+ + 2 e- Hg

Hg + 2 ClEo = + 0.27 V
Eo = + 0.85 V.

Calculate the Ksp for HgCl2.

Oxidation Hg Hg2+ + 2 e
Reduction
Overall

E0 = 0.85 V

HgCl2 + 2 e- Hg + 2 Cl-

HgCl2 Hg2+ + 2 Cl-

Ecell = 0.58 V

0.059
EE
lg K sp
n
0

0 0.58 V

E0 = + 0.27 V

0.059
lg K sp
2

lg Ksp = 19.66
Ksp = 2.18 x 10-20 mol3 dm-9

13.7.3 Nernst Equation and pH of a Solution

Under SHE, if the solution of H+ is not 1.00 mol dm-3, the Ecell
can be calculated using Nernst equation.

H2 (g)
1.0 atm
Salt
bridge
(made of
saturate
d KCl /
Standard hydrogen electrode
NaCl)

M (s)

H+ (aq)
[x M]
25oC

M2+ (aq)
[1.0 M]
Zinc half cell

Assuming the metal is oxidise by SHE, the cell notation is

written as
M (s) I M2+ (aq) II H+ (aq) (x mol dm-3) , H2 (g) I Pt (s)

 The overall reaction can be written as

M (s) + 2 H+ (aq) M2+ (aq) + H2 (g) E0 = + a V

x
0
.
059
[
reac
tan
t
ions
]
E E0
lg
n
[product ions]y

2
0
.
059
[
H
]
E E0
lg 2 1
2
[M ]

0.059
[H ]
E E
2 lg
2
[1]
0

E E 0 0.059 pH

Example : The e.m.f. of of the following cell at 25 oC is 0.093 V

Pb (s) I Pb2+ (1.00 mol dm-3) II H+ (test solution), H2 (g) I Pt (s)
Calculate the pH of the solution
Overall equation : Pb + 2 H+ Pb2+ + H2 E0 = + 0.13 V

E = E0 0.059 pH
0.059 pH = + 0.13 0.093
pH = 0.63
Calculate the e.m.f. of the chemical cell compared relatively to
SHE at [H+] = 0.0030 mol dm-3 for a calcium half cell.

2.9

Type of cell.

A battery is a galvanic cell, or a series of combined galvanic cells,

that can be used as a source of direct electric current at a

constant voltage.
Although the operation of a battery is similar in principle to that of

the galvanic cells. A battery has the advantage of being completely

self-contained and requiring no auxiliary components such as salt
bridges.
Here we will discuss several types of batteries that are in

widespread use.
Lithium ion battery
Fuel Cell

2.9.1

Lithium ion battery

Figure below shows a schematic diagram of a lithium-ion battery.

During the discharge of the battery,

the half-cell reactions are
Anode : Li(s) Li+ + eCathode : Li+ + CoO2 + e- LiCoO2 (s)
Overall : Li (s) + CoO2 LiCoO2 (s)
Ecell = + 3.4 V

The anode is made of a conducting carbonaceous material, usually

graphite, which has tiny spaces in its structure that can hold both Li
atoms and Li+ ions.

 The cathode is made of a transition metal oxide such as

CoO2, which can also hold Li+ ions. Because of the high
reactivity of the metal, non - aqueous electrolyte (organic
solvent plus dissolved salt) must be used.
The advantage of the battery is that lithium has the most
negative standard reduction potential and hence the greatest
reducing strength. Furthermore, lithium is the lightest metal
so that only 6.941 g of Li (its molar mass) are needed to
produce 1 mole of electrons.
A lithium-ion battery can be recharged literally hundreds of
times without deterioration. These desirable characteristics
make it suitable for use in cellular telephones, digital
cameras, and laptop computers.

2.9.2 Fuel Cell

Fossil fuels are a major source of energy, but conversion of
fossil fuel into electrical energy is a highly inefficient process.
Consider the combustion of methane:
CH4 (g) + 2 O2 (g) CO2 (g) + 2 H2O (l) H = - x kJ mol-1
To generate electricity, heat produced by the reaction is first
used to convert water to steam, which then drives a turbine
that drives a generator.
An appreciable fraction of the energy released in the form of
heat is lost to the surroundings at each step; even the most
efficient power plant converts only about 40 percent of the
original chemical energy into electricity.
Combustion reactions are redox reactions, it is more desirable
to carry them out directly by electrochemical means, thereby
greatly increasing the efficiency of power production

 This objective can be accomplished by a device known as a

fuel cell, a galvanic cell that requires a continuous supply of

reactants to keep functioning.
In its simplest form, a hydrogen-oxygen fuel cell consists of an
electrolyte solution, such as potassium hydroxide solution,
and two inert electrodes. Hydrogen and oxygen gases are
bubbled through the anode and cathode compartments where
the following reactions take place.

Anode : 2 H2 (g) + 4 OH- (aq) 4 H2O (l) + 4 e- Eo = + 0.83 V

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

Eo = + 0.40 V

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

Eocell = + 1.23 V
The electrodes used have a two-fold function. They serve as
electrical conductors, and they provide the necessary
surfaces for the initial decomposition of the molecules into
atomic species, prior to electron transfer. They are also known
as electrocatalysts. Metals such as platinum, nickel, and
rhodium are good electrocatalysts.

2.9.2.1 Propane-oxygen fuel cell

In addition to the H2-O2 system, a number of other fuel cells
have been developed. Among these is the propane-oxygen
fuel cell.
The half-cell reactions are
Anode : C3H8 (g) + 6 H2O (l) 3 CO2 (g) + 20 H+ (aq) + 20 eCathode : 5 O2 (g) + 20 H+ (aq) + 20 e- 10 H2O (l)
Overall

: C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)

Unlike batteries, fuel cells do not store chemical energy.

Reactants must be constantly resupplied, and products

must be constantly removed from a fuel cell. In this respect,
a fuel cell resembles an engine more than it does a battery.
However, the fuel cell does not operate like a heat engine
and therefore is not subject to the same kind of
thermodynamic limitations in energy conversion

 Properly designed fuel cells may be as much as 70 percent

efficient, about twice as efficient as an internal combustion

engine. In addition, fuel-cell generators are free of the noise,
vibration, heat transfer, thermal pollution, and other
problems normally associated with conventional power
plants.

2.10 Electrolysis ~ decomposition of a

substance by direct current electricity.
Electrolyte substance that can conduct electricity
when in aqueous solution or in molten state
Electrolytic cell cell consisting of 2 electrodes
immersed in an electrolyte for carrying out
electrolysis In an electrolytic cell, the following apply
anode
Positive terminal is called as
whereas the
negative terminal iscathod
called as
At anode,oxidatio
. eprocess occur where
n reductio
as at cathode,
..process occur
n
cathode
Cations are attracted
to
.. while
anode
anions are attracted to

anode
Electrons flow from the
to
cathode in the external circuit.
....
A

2.11 Faradays Law

Faradays Law stated that 1 Faraday is the quantity of
electricity (9.65 x 104 C) that must be supplied to an
electrolytic cell in order to produce one mole of
electrons for reactions in the cell.
The extension of Faraday Law is stated in Faradays First
Law, where it stated that the proportiona
mass of a substance
l electrolysis is .
produced at an electrode during
to the quantity of electricity (in Coulumb) passed. From the
statement above, the factors that influence the mass of a
substance liberated during electrolysis are
The greater the number of electrons transferred, the
greater the mass of the product.
The longer the time taken, the greater the electrical
current produced, the more the mass produced
Based on the statement above, the quantity of electrical
current can be calculate according to time where

Q = It

Example 1 : Calculate the mass of silver

formed when a current of 0.200 A is applied to
a electrolytic cell filled with aqueous silver
nitrate for 2 hour.
Q = It @ Q = (0.200)(2 x 60 x 60)
= 1440 C
Eq : Ag+ + e- Ag
mol of e- = Q / F @ mol = 1440 /
96500
mol of e- = 0.0149 mol
Since 1 e- = 1 Ag ; mol Ag = 0.0149
mol
Example
3 :=
Calculate
Mass Ag
0.0149the
x mass
108 of chromium
formed=when
1.20
1.61
g A of current is directed into
molten chromium (III) chloride for 3 hours.
Q = It @ Q = (1.20)(3 x 60 x 60)
= 12960 C
Eq : Cr3+ + 3 e- Cr
mol e- = Q / F @ mol = 12960 /
96500
mol of e- = 0.134 mol
Since 3 e- = 1 Cr ; mol Cr = 0.0448
mol
Mass Cr = 0.0448 x 52.0

Example 2 : An aqueous solution of copper (II)

sulphate is electrolysed using a current of 0.50
A for 4 hours. Calculate the mass of Copper,
Cu deposited at cathode.
Q = It @ Q = (0.50)(4 x 60 x 60)
= 7200 C
Eq : Cu2+ + 2 e- Cu
mol of e- = Q / F @ mol = 7200 /
96500
mol of e- = 0.0746 mol
Since 2 e- = 1 Cu ; mol Cu = 0.0373
mol
Example
4 : Calculate
time taken to
Mass Cu=
0.0373 the
x 63.5
produce
= 18.0
2.4 ggof silver from silver nitrate by a
current of 0.900A
Mol of Ag = 18.0 / 108 = 0.167
mol
Eq : Ag+ + e- Ag
1 Ag = 1 e- ; so mol e- = 0.167 mol
Q = mol e- x F @ Q = 0.167 x
96500 Q = 16083 C
Q = It @ t =16083 / 0.900
t = 1.78 x 104 s

Example 5 : Calculate the time required to Example 6 : Calculate the time required to
form 200g of lead from molten lead (II)
form 10 g of aluminium from molten
bromide by a current of 1.50 A.
aluminium oxide by a current of 10 A

Mol of Pb = 200 / 207

= 0.966 mol
Eq : Pb2+ + 2 e-
Pb
1 Pb = 2 e- ; so mol e= 1.93 mol
Q = mol e- x F @
Q = 1.93 x 96500
Q = 186473 C
Q = It @ 186473 / 1.50
t = 1.24 x 105 s

Mol of Al = 10 / 27
= 0.370 mol
Eq : Al3+ + 3 e- Al
1 Al = 3 e- ; so mol e= 1.11 mol
Q = mol e- x F @
Q = 1.11 x 96500
Q = 107222 C
Q = It @ t =
107222 / 10
t = 1.1 x 104 s

14.2.1 Faradays Second Law

~ stated that if the same quantity of electricity is
passed through different electrolytes, the mass of
substance liberated at electrode is inversely
proportional to the charge of ions.
1 Faraday

Silver (I)
nitrate

Copper (II)
sulphate

Chromium (III)
chloride

Sulphuric acid

Half equation occur at cathode for

Type of
electrode

Half equation

Mol of metal
deposited

Silver

Ag+ (aq) + e- Ag (s)

Copper

Cu2+ (aq) + 2 e- Cu (s)

1/2 mol

Carbon in CrCl3

Cr3+ (aq) + 3 e- Cr (s)

1/3 mol

Carbon in
H2SO4 (occur at
anode)

1 mol

Mol of non-metal

2 H2 O O 2 + 4 H + + 4 e

1/4 mol

1 . mol of
From the diagram above, 1 F will discharge
1/2 ; mol of Cu2+
1/3
1/4
3+ ion ;
Ag+ ions
ion ; mol of Cr
. mol of O2.

Example 7 : Calculate the mass of copper

deposited under the same cell if the
amount of silver formed under the same
amount of quantity charge is 1.8 g.

Mol of Ag = 1.8 / 108

= 0.01667 mol
Eq : Ag+ + e- Ag
Since 1 Ag = 1 e- ;
mol e- = 0.01667 mol
For Cu ; Cu2+ + 2 e Cu
Since 2 mol e- = 1 mol Cu
So mol of Cu = 0.008333 mol
Mass of Cu = 0.008333 x 63.5
= 0.53 g

An electric current produced 0.56 g of

aluminium from molten aluminium
oxide. If the same current was used to
electrolysed molten lead (II) bromide,
calculate the mass of lead deposited.

Mol of A1 = 0.56 / 27
= 0.02074 mol
Eq : Al3+ + 3 e- Al
Since 1 Al = 3 e- ;
mol e- = 0.06222 mol
For Pb ; Pb2+ + 2 e Pb
Since 2 mol of e = 1 mol of Pb
So mol of Pb = 0.03111 mol
Mass of Pb = 0.03111 x 207
= 6.44 g

Predicting the product for electrolysis

In electrolysis, there may be more than one type of
cation / anion inside the electrolytes.
Under such circumstance, since an electrode can only
discharge one cation / anion, the ion must be choose
under certain guidelines.
The selectivity of ions are based on electrochemical
series

No matter it is an electrolytic cell or chemical cell,

At anode,oxidation
. reaction occur ; electrons donated
are
reduction
received

molten
At cathode, . reaction occur ; electrons
are
aqueous

Electrolytes can only discharge under 2 conditions : .....

state or solution.
When in molten state, the electrolytes contain only the
cation and anion of the substance involve
Molten lead (II) bromide
: PbBr2 (l) Pb2+ + 2 Br
Molten aluminium oxide

: Al2O3 (l) 2 Al3+ + 3 O2

Molten barium chloride : BaCl2 (l) Ba2+ + 2 Cl

Molten silver (I) iodide : AgI (l) Ag+ + I

Electrolyte

PbBr2 (l)

Al2O3 (l)

NaCl (aq)

Subst.
present

Pb2+
Br

Al3+
O2

Na+
Cl

Half equation at anode

Br2 + 2e-
2BrE0 = +
1.07 V
Rev:
2Br- 2e- +
Br2
O2 + 4e-
2O2E0 = ? V
Rev:
2O2- O2 +
4eCl2 + 2e-
2ClE0 =
+1.36 V
Rev:

Substance
at anode

Half equation at
cathode

Pb2+ + 2e-
bromine
Pb
E0 = 0.13
V

oxygen

Substance
at cathode

lead

Al3+ + 3e- Al Alumin

E0 = 1.67
um
V

Na+ + e- Na
chlorine
E0 = 2.71 Sodium
V

No matter it is an electrolytic cell or chemical cell,

At anode,oxidation
. reaction occur ; electrons donated
are
reduction
received

At cathode, . reaction occur ; electrons are

When in aqueous solution, not only it contains the cation and

anion of substance involve,
but it also involves water. thus
positive
there is a selectivity of ion occur negative
In the terms of E0, a more .. value will be selected for
+ 1.23
discharge at4cathode,
while
. value
will be
H + + O2 +
4 e amore
2 H 2O
0.83
H2O + 2 at
e anode.
2 OH +
selected for2discharge
At anode : H2
E0 = . V
At cathode :
E0 = . V
However, water is a weak electrolytes. At 250C and 1 atm, the
E0 value varies with the solution used. So in deciding which E 0
value we should used, we need to consider if the solution is
+ 0.81
different or 4not.
H + + O2 + 4 e 2 H 2O
0.41

Under neutral
[H+]+= [OH-], usingNernst
2 Hcondition,
2 OH
2O + 2 e where
+
-7
-3
Equation, EoHvalues
are
(At
[H
]
=
[OH
]1.0
x
10
mol
dm
)
2
At anode :
E0 = .. V

Electrolyt
e

NaCl (aq)

Subst.
present

Na+
Cl
H 2O

Half equation at anode

Cl2 + 2e-
2ClE0 =
+1.36 V
4 H + + O2 + 4
e 2 H2O
E0 =
+1.23 V
Rev: 2 H2O
4 H + + O2 + 4
e

Substance
Substance
Half equation at cathode
at cathode
at anode

Na+ + e- Na
E0 = 2.71
oxygen V
2 H 2O + 2 e

2 OH +
H2
E0 = 0.83
V

Hydrog
en

Electrolyte

Ions
Half equation at anode Substance
present

CuSO4 (aq)

Cu2+
SO42
H 2O

PbI2 (aq)

Pb2+
I
H 2O

KOH (aq)

K+
OH
H 2O

Half equation at
cathode

Substance

S2O82- +2e-
Cu2+ + 2e-
2SO42Cu
E0 = +2.01
E0 = +
Copper
oxygen
V
0.34 V
+

4 H + O2 + 4 e
2 H 2O + 2 e
2 H2O

0
E = +1.23
2 OH +
2+
V
I2 + 2 e- 2 IPb
H2 + 2e-
0 2O
Rev: 2EH
= +0.54
Pb E0 = 0.83
0
V 4 H+ + O2 + 4
E
= 0.13
Lead
V
iodine
+

4
e H + O 2 + 4 e
V
2 H2O
2 H 2O + 2 e
E0 = +1.23

O
+
2
H
O
+
4
eV2
2
2 OH +

Rev:2 4
I OH
I2 + 2
K + e- K
H2
E0 = + 0.40
e
E00 = 2.92
E = 0.83
V
V
hydroge
4 H+ + O2 + 4 e oxygen V

2 H 2O + 2 e
n
2 H2O

0
E = +1.23
2 OH +

Effect on concentration towards the selectivity of the

ions to discharge
In general, an ion with a very high concentration is
preferentially discharged.
For example if Pb2+ ion and Cu2+ ion are mixed
Cu2+
under the same concentration,
ion is
preferred to be discharge at cathode as it has a
lower position in electrochemical series.
However, if the concentration of Pb2+ ion
2+
Pb
concentration is raised much higher than Cu2+ ion,
. ion is more readily to be discharged.
Another example is potassium chloride in aqueous
H2..
O
solution. Under dilute solution of KCl,
will be
selected at anode andoxygen
... gas is given out,
as it has a lower position in electrochemical series.

 However, if concentrated KCl is used as electrolyte,

Cland is selected
the concentrated of Cl- increase,
chlorine
to be discharge
and ... gas is given out.
Still, if the position in electrochemical series differ
too much, like K+ and water in the example above,
+ ion
not
Kwill
be discharge as the position is
hydrogen
much too high.
At the end, . gas is given
out at cathode.
If chloride ion is replaced with fluoride
water ion, F ion,
and concentration of F very
ion ishigh
increased, ....... is
still be preferred as F ion has a . position
in electrochemical series
In the table below, predict the element that is
expected to form when electrolyse.

Electrolyte

Concentrate
NaCl

Concentrated
PbBr2

Concentrated
LiF

Ions
present

Na+
Cl
H 2O

Pb
Br
H 2O

2+

Li+
F
H 2O

Half equation at
anode

Substance

Half equation at
cathode

Na+ + e- Na
Cl2 + 2e- 2ClE0 = 2.71
E0 =
+1.36 V
V
chlorine
4 H+ + O2 + 4 e
2 H 2O + 2 e
2 H2O

0
E =
2 OH +
+1.23 V
H2
4
H+ 2+ClO- 2+ 4
Rev:
2+ E0 = 0.83

Pb
+ 2e-
e Cl2
H
O
2e
2 +2

Substance

Hydrog
en

V
Pb
E0 =
bromine
E0 = 0.13
lead
+1.23 V
V
Br2 + 2e-

2
H
O
+
2
e
2
2Br+
0
Li +2 e Li
F2 + E
2e-=+2FOH
+
1.07 VE0 =
0
E
=

3.04
H2
Rev:
+2.87 V
V
Hydrogen
0
oxygen
E
=

0.83
+ 2e +

2Br
4 H + O2 + 4 e
2 H 2O + 2 e
V
Br
2 2 H2O

0
E =
2 OH +
+1.23 V

2.12.3
Overvoltage
Overvoltage ~ the difference between electrode
potential and discharge potential. In another words,
Overvoltage is the voltage that must be applied to an
electrolytic cell in addition to the theoretical voltage to
cause an electrode reaction to occur.
Example of over voltage phenomenon is the
electrolysis of aqueous sodium chloride. Consider the
electrolysis of sodium chloride in aqueous solution
where the substance presence are Na+, Cl-, H2O
Half equation for substance attracted to
anode
Cl2 (g) + 2 e- 2 Cl- (aq) E0 = + 1.36 V
4 H+ + O2 (g) + 4 e- 2 H2O (l)
E0 = + 0.81 V
(conc. H+ = 1 x 10-7 mol dm-3)

Half equation for substance attracted to

cathode
Na+ (aq) + e- Na (s)
E0 = - 2.71 V
2 H2O (l) + 2 e- 2 OH- + H2 (g)
E0 = - 0.41 V
(conc. OH- = 1 x 10-7 mol dm-3)

From the E0 values at anode, it is suggested that H2O

should be preferentially oxidized at the anode.
However, by experiment we find that the gas
liberated at the anode is Cl2, not O2.
In studying electrolytic processes, we sometimes find
that the voltage required for a reaction is considerably
higher than the electrode potential indicates.
The overvoltage is the difference between the
electrode potential and the actual voltage required to
cause electrolysis. In this case, overvoltage for O2
formation is quite high. Therefore, under normal
operating conditions Cl2 gas is actually formed at the
anode instead of O2.
As for the selectivity at cathode, H2O is selected since
the E0 value for H2O is less negative than Na+.

Thus the half equation occur at both anode and

cathode are

Anode
Cathode
Overall
As the overall reaction shows, the concentration of
the Cl2 ions decreases during electrolysis and that of
the OH- ions increases.
Therefore, in addition to H2 and Cl2, the useful byproduct NaOH can be obtained by evaporating the
aqueous solution at the end of the electrolysis.

2.12.4 Electrorefining and electroplating

The purification of a metal by means of electrolysis is
called electrorefining. For example, impure copper
obtained from ores is converted to pure copper in an
electrolytic cell that has impure copper as the anode
and pure copper as the cathode. The electrolyte is an
aqueous solution of copper sulphate

At the impure Cu anode, copper is oxidized along with

more easily oxidized metallic impurities such as zinc
and iron. Less easily oxidized impurities such as silver,
gold, and platinum fall to the bottom of the cell as
anode mud, which is reprocessed to recover the
precious metals. At the pure Cu cathode, ions are
reduced to pure copper metal, but the less easily
reduced metal ions (and so forth) remain in the
solution
Half equations occur for electrorefining process of
copper above are
At anodeCu (s) Cu2+ (aq) + 2 e At cathode Cu2+ (aq) + 2 e- Cu (s)
Thus, the net cell reaction simply involves transfer of
copper metal from the impure anode to the pure
cathode, hence purified the copper.

Closely related to electrorefining is electroplating,

the coating of one metal on the surface of another
using electrolysis. For example, steel automobile
bumpers are plated with chromium to protect them
from corrosion, and silver-plating is commonly used to
make items of fine table service.
The object to be plated is carefully cleaned and then
set up as the cathode of an electrolytic cell that
contains a solution of ions of the metal to be
deposited (as shown in diagram above)
Half equations occur for electroplating process of
silver above are
At anodeAg (s) Ag+ (aq) + e At cathode Ag+ (aq) + e- Ag (s)

2.13
Industrial Electrolysis :
In this Chapter, we shall discussed the manufacturing of
aluminium and chlorine gas using the principle of
electrolysis
Part 1 : Getting pure aluminium oxide (alumina) from
bauxite.
1st step: Removal of impurities from the ore by dissolving
Al2O3 + in
2 NaOH
+ 3 H2O 2sodium
powdered bauxite
hot concentrated
NaAl(OH)
hydroxide
solution.4

SiO2 + 2 NaOH Na2SiO3 + H2O

2nd step: Insoluble impurities are filtered off. Filtrate contain
aluminium and silicon ions. Aluminium ion is
precipitated as aluminium hydroxide which is filtered
Uselater
acidas white
: 2 [Al(OH)
2 H+ 2 Al(OH)3 + 2 H2O
out
gelatinous
precipitate.
4] +

Or use CO2 : 2 [Al(OH)4]- + CO2 2 Al(OH)3 + H2O +

CO32-

3rd step: Aluminium hydroxide is filtered, washed, dried and

finally heated out to 12000C to produce pure aluminium
oxide (alumina),2AlAl(OH)
3 Al2O3 + 3 H2O
2 O3

Part 2
:
Extracting aluminium out from aluminium
oxide
Hall-Heroult process:- A process of electrolysing aluminium
oxide (alumina) to extract out aluminium.
Aluminium metal is extracted by the cell electrolytic
reduction of alumina. Melting point of alumina is 20300C. To
lower the temperature of the electrolyte, alumina is
dissolved in molten cryolite (Na3AlF6), to maintain a
temperature at about 9600C.
When alumina dissolve in molten cryolite :

Al2O3 (s) 2 Al3+ (l) + 3 O2 (l)

Electrolyte mixture is then placed in carbon-lined iron

vat (cathode). The heating effect of the electric
current melts the electrolyte mixture, producing Na+,
Al+3+, O2-- and F- ions.
Na + e Na E0 = 2.71 F2 + 2 e- 2 F- E0 = +
V
2.87 V
Al3+ + 3e- Al E0 = 1.66 O2 + 4e- 2O2- E0 = +
V
1.++V
Half equation occur at cathode
Half equation occur at anode

Al3+ + 3e- Al E0 = 1.66 2O2- O2 + 4e- E0 = +

V
1.++V

Aluminium alloy parts are anodized to greatly

increase the thickness of this layer for corrosion
resistance. The corrosion resistance of aluminium
alloys is significantly decreased by certain alloying
elements or impurities : copper,iron, andsilicon, tend
to be most susceptible.
By making an aluminium the anode of cell in which
dilute sulphuric acid is the electrolytes, it is possible to
produce a thicker and harder film of aluminium oxide
on the surface of metal.
Al

2.13.1.2
Recycling aluminium
Environmental pollution arises as cans are littered
everywhere.
The best solution of environmental pollution is
recycling.
The benefits of recycling can be seen by comparing
the energy consumed in the extraction of aluminium
from the bauxite or using Hall process with that
consumed when aluminium is recycle.

Pure aluminium has a rather low melting print of

6600C, thus requiring only 26.1 kJ mol-1 of energy.
On comparison between the Hall process and
recycling,
Energy used in recycling = 26.1 297 100%
= 8.8%
This means that about 91% of the energy is
saved for every 1 mole of the aluminium produced
through recycling

In industrial process, chlorine gas, together with

sodium metal, is prepared using molten sodium
chloride (brine) using mercury-cathode cell.
Half equation occur at cathode

Half equation occur at anode

2Cl- Cl2 + 2e- E0 =

Na+ + e- Na
E0 =
2.71 V
1.36 V
Mercury is specially used to attract the sodium formed
in cathode and form an alloy named amalgam
This method is not environment friendly as the
mercury used is poisonous.

Similar to the mercury-cathode cell, the electrolytes

brine
(sodium
chloride)
used in diaphragm cell
is also
..
The process inside the diaphragm cell is known as the
chlor-alkali process.

When sodium chloride dissociates under the effect of

an electric current, the chloride ions are discharged.
Half equation
2 Cl-: Cl2 + 2 e-

Titanium is chosen as the anode because it resists

corrosion by the very reactive chlorine
At cathode, since the sodium ion (Na+) is attracted to
cathode through the diaphragm, the selectivity to
discharge is between sodium ion and water molecule.
Standard reduction potential of sodium :
Na+ + e- Na
E0 = 2.71 V
Standard reduction potential of water :
2 H2O + 2 e 2 OH + H2
E0 =
water
water
Since

has a higher E0 value,

is
0.83
V
hydrogen
discharge
and is produced.
gas of brine (left or anode position) is always
The level
placed higher than the water (right or cathode
prevent water
from crossing to brine portion. This
position)
to ..
will dilute the solution and chlorine will not be
......
discharged.

13.8 Corrosion of metal

Corrosion is the oxidative deterioration of a metal, such as
metal
metal oxide
the conversion of ...
to ..
2 main important components for rusting are
oxygen
water
..
and
A possible mechanism for rusting, consistent with the known
facts, is illustrated in Figure below

In alkaline / neutral condition

At anode :
At cathode :
Fe (s) Fe2+ (aq) + 2e- Eo = +0.44 V O2(aq) + 2H2O(l) + 4e 4OH(aq)
Eo = + 0.40 V
2 Fe (s) + O2 (aq) + 2 H2O 2 Fe2+ + 4 OH [or 2 Fe(OH)2]

Ecell = + 0.84 V

Fe(OH)2 (aq) + OH Fe(OH)3 + e O2(aq) + 2H2O(l) + 4e 4OH(aq)

Eo = + 0.40 V
Eo = +0.56 V
4 Fe(OH)2 (aq) + O2(aq) + 2H2O(l) 4 Fe(OH)3 (aq) Ecell = + 0.96 V
Forming rust : 2 Fe(OH)3 (s) Fe2O3.x H2O + (3 x) H2O

 In acidic condition
At anode :
At cathode :
Fe (s) Fe2+ (aq) + 2e- Eo = +0.44 V O2(aq) + 4 H+(aq) + 4e 2H2O(l)
Eo = + 1.23 V
2 Fe (s) + O2 (aq) + 4 H+ 2 Fe2+ + 2 H2O
At anode :
Fe2+ (aq) Fe3+ (aq) + eEo = -0.77 V

Ecell = + 1.67 V

At cathode :
O2(aq) + 4 H+(aq) + 4e 2H2O(l)
Eo = + 1.23 V

4 Fe2+ (aq) + O2 (aq) + 4 H+(aq) 4 Fe3+ (aq) + 2H2O(l)

Ecell = + 0.46 V

Forming rust : 2 Fe3+ (aq) + 4 H2O (l) Fe2O3.H2O (s) + 6 H+ (aq)

13.8.2 Prevention of rusting

Various methods are used to prevent / slowing down rusting.
Methods

Explanation
Iron is alloyed with nickel and chromium to form .
Stainless steel
The chromium forms an impervious oxide layer on the surface of

Alloying

iron increasing its resistance to corrosion. Chromium at the same

time .. the steel

decorated / coated

Painting the iron object

Barrier

Use grease / oil to coat the moving parts of machine

Coating ironwith chromium (plating) or zinc (galvanising)
Also known as
anodic protection
Metal with a . position in electrochemical series is

higher

Sacrificial

connected to iron. Under such way, ... Will be

oxidised first before iron.

reactive metal

AdditionalSlide (from
old syllabus)

 13.7.4 Effect of pH on Electrode Potential of a Half cell

Some reaction involve H+ ions. Examples of the are

14 H+ + Cr2O72- + 6 e- 2 Cr3+ + 7 H2O

8 H+ + MnO4- + 5 e- Mn2+ + 4 H2O
6 H+ + ClO3- + 6 e- Cl- + 3 H2O
Under standard conditions, the [H+] is 1.00 mol dm-3. varying the

concentration of [H+] and hence its pH, would change the

electrode potential of the half cell.
Consider the following half cell reaction :

MnO4- (aq) + 8 H+ (aq) + 5 e- Mn2+ (aq) + 4 H2O (l) E = + 1.52 V

Using Nernst Equation, Ecell can be expressed as

0.059
[MnO 4 ][H ]8
E 1.52
lg
5
[Mn 2 ]
When [MnO4-] = [Mn2+] = 1.00 mol dm-3 ; Ecell =

E 1.52

0.059
8 lg [H ]
5

E 1.52 0.0944 pH

[H+] / mol dm-3

1.0

0.1

0.01

0.00001

pH

Ecell (V)

+ 1.52

+ 1.43

+ 1.33

+1.05

It is then compare to the standard electrode potential of chlorine, bromine

and iodine
Cl2 + 2 e- 2 Cl- Eo = + 1.36 V @ 2 Cl- Cl2 + 2 e- Eo = - 1.36 V
Br2 + 2 e- 2 Br- Eo = + 1.07 V @ 2 Br- Br2 + 2 e- Eo = - 1.07 V
o
I2 + 2 e- 2 I- Eo = + 0.54 V @ 2 I- I2 + 2 eV
-E = -- 0.54
Cl , Br , I+ 1.43
are
Under pH = 1 , Ecell of manganate (VII) ion is ................ V
oxidising
oxidise
able to by manganate (VII) ion as it is still a strong
agent.
+ 1.33
Br- , I2, Ecell of manganate (VII) ion is ..............
V. Only
Under pH = oxidise
Clare able to
by manganate-(VII)
spontaneous
0.03ion.
V cannot oxidise as the
reaction is not (Ecell = )+ 1.05
I= 5, Ecell of manganate (VII) ionClis- ,..............
V. Only are
Br Under pH
oxidise
spontaneous
V for Brcannot
able to
by manganate (VII)-0.03
ion. .
oxidise as the
-0.31 V for Clreaction is not (Ecell = )

Primary cell

Dry cell

Alkaline cell

Diagram

Anode
Equation occur
at anode
Cathode
Equation occur
at cathode
Electrolytes

zinc
Zn Zn

2+

+ 2e

zinc

Manganese (IV) oxide

2 MnO2 + 2 NH4+ 2 e-
Mn2O3 + 2 NH3 + H2O
Ammonium chloride and
zinc chloride paste

Zn + 2OH
H2O + ZnO + 2 e
Manganese (IV) oxide
2 MnO2 + 2 H2O + 2 e-
Mn2O3 + 2 OH
Potassium hydroxide

Primary
cell

Mercury cell

Lead acid accumulator

Diagram

Anode
Equation
occur at
anode

Zinc
Zn + 2OH
H2O + ZnO + 2 e

Cathode

Mercury (II) oxide

Equation
occur at
cathode

HgO + H2O + 2 e-
Hg + 2 OH

Electrolyt
es

Potassium hydroxide

Lead
Pb + HSO4
PbSO4 + H+ + 2 e
Lead (IV) oxide

PbO2 + 3 H+ + HSO4 + 2 e
PbSO4 + 2 H2O
Sulphuric acid

Fuel Cell

Lithium ion cell

Anode

Hydrogen

Lithium metal

Equation
occur at
anode

2 H2 + 4 OH 2 H2O + 4 e

Li (s) Li+ (aq) + e-

Cathode

Oxygen

Manganese (IV) oxide

Diagram

Equation
occur at
cathode
Electrolytes

O2+ 2 H2O + 4 e 4 OH
Hot potassium hydroxide (aq)

MnO2 (s) + Li+ + e-

LiMnO2
Lithium chlorite (VII), LiClO4

13.9

Dental Filling

amalgam (a
The material commonly used to fill decaying teeth is an .

mercury

base alloy). The component in dental filling of amalgam are

tin
mercury
silver
. , and ..

The standard electrode potential of these electrode system are :

Hg22+ (aq) / Ag2Hg3 (s) Eo = + 0.85 V

Sn2+ (aq) / Ag3Sn (s) Eo = 0.55 V
Sn2+ (aq) / Sn8Hg (s) Eo = 0.13 V

The diagram shows the reaction take place when gold is contact with dental
dental amalgam

amalgam, which result a electrochemical

goldcell. act as the
anode
saliva of the cell, while act as the cathode and .. act as the
electrolyte.

positive

Since tin is more electro than gold, hence tin will corrode to

form Sn2+ and mixed with saliva. This will result an unpleasant taste in the
mouth.
If the dental amalgam is in contact with an aluminium foil, an electrochemical

electropositive
cell
will also produced. Unlike gold, aluminium is more .. than
any of the electrode above,anode
which makes aluminium servesamalgam
as an
of the cell, while . as the cathode of cell. This
will result a weak current flow between the electrode and cause an unpleasant
sensation in the tooth.