1

ELECTROCHEMISTRY
Electrode
Half cell
Types of Electrode
Electrodes potential
Types of Electrochemical cell
Cell Potential

2
Electrodes and Half Cell
When a metal is immersed in metal
ion solution it formed half cell.

M
(p)
M
n+


M
electrode
Ions
solution of
M
n+

Half cell
3
Electrodes and Half Cell
Combination of two half cell form a
electrochemical cell
V
Metal
Y
Ion Y
n+

Ion X
m+

Metal X
Salt
bridge
e
-

Anode cathode
4
Electrodes and Half Cell
Anode oxidation
Cathode reduction
Reaction in anode:
X (p) X
m+
(aq) + me
-


Cathode :
Y
n+
(aq) + ne
-
Y (p)

5
Electrodes and Half Cell
Overall cell reaction :
X
(p)
+ Y
n+

(aq)
X
m+

(aq)
+ Y
(p)


me
-
= ne
-


6
Types of electrode
Refference electrode
Standard hydrogen electrode (SHE)
H
2
, 1 atm
H
+
, 1 M
Pt
298 K
7
Types of electrode
Reaction :
2H
+
(aq) + 2e
-
H
2
(g)

Symbol :H
+
|H
2
|Pt

Nernst equation:
2
2
| |
ln
2
2 2
+
+ +
=

H
H H H H
a
fH
F
RT
E E
8
Types of electrode
Silver-silver chloride electrode
A silver chloride is in contact with
solid silver chloride, which is highly
insoluble salt.
The whole is immersed in potassium
chloride solution which the chloride
ion concentration is 1 M

9
Types of electrode
Reaction:
AgCl
(s)
+ e
-
Ag
(s)
+ Cl
-

(aq)


Symbol :Cl
-
|AgCl|Ag

Nernst equation:



= aCl
zF
RT
E E
Cl Ag AgCl Cl Ag AgCl
ln
| | | |
10
Types of electrode
Combination with SHE
Pt|H
2
(1 atm)|H
+
(1M)||Cl
-

(1M)|AgCl|Ag

Anode
H
2
H
+
+ e
-


Cathode
e
-
+ AgCl Ag + Cl
-
11
Types of electrode
Overall reaction:
H
2

(g)
+ AgCl
(s)
H
+

(aq)
+ Cl
-

(aq)
+ Ag
(s)


E.m.f = 0.2224V
12
Types of electrode
Calomel electrode
mercury is in contact with mercurous
chloride (Hg
2
Cl
2
, calomel) which is
immersed in 1 M of potassium
chloride or in saturated solution of
potassium chloride

Reaction :
Hg
2
Cl
2

(s)
+ e
-
Hg
(s)
+ Cl
-

(aq)
13
Types of electrode
Symbol :Cl
-
|Hg
2
Cl
2
|Hg
Combination with SHE
Pt|H
2
|H
+
(1M)||Cl
-
(1M)|Hg
2
Cl
2
|Hg

Anode
H
2
(g) H
+
(aq) + e
-


Cathode
Hg
2
Cl
2

(s)
+ e
-
Hg
(s)
+ Cl
-
(aq)
14
Types of electrode
Overall reaction
H
2

(g)
+ Hg
2
Cl
2

(s)
H
+
(aq)
+ Hg
(s)
+ Cl
-

(aq)


E.m.f = 0.3338 V (KCl = 1 M)
E.m.f = 0.2415 V (saturated KCl)
15
Types of electrode
Redoxs electrodes

Symbol :Fe
3+
|Fe
2+
|Pt
Reaction :
Fe
3+

(aq)
+ e Fe
2+

(aq)
16
Electrode Potential
Comparison with SHE (0 V)

Reduction potential of half cell
known as standard reduction
potential, E
0


17
E
0
(+ve)
E
0
(-ve)
2H
+
(aq) + 2e
-
H
2
(g),E =0V
Reduction agent
anode
Oxidation agent
cathode
18
Types of electrochemical cell
Concentration cell
Different in electrolytes cocentration
E.g :
Pt|H
2
|HCl (m
1
)|HCl (m
2
)|H
2
|Pt

Left reaction :
H
2
H
+
(m
1
) + e
-
19
Types of electrochemical cell
right reaction:
H
+
(m
2
) + e
-
H
2


Overall reaction:
H
+
(m
2
) H
+
(m
1
)

m
2
> m
1
.
1
2
ln
m
m
zF
RT
E =
20
Concentration cell

H
2

H
2

H
+
(m
1
)
H
+
(m
2
)
Cl
-
Cl
-

V
Porous plug
Anode
oxidation
Cathode
reduction
21
Redox cell

Pt|H
2
|H
+
(1M)|Fe
2+
|Fe
3+
|Pt

Left reaction
H
2
H
+
+ e
-


Right reaction
e
-
+ Fe
3+
Fe
2+
22
Overall reaction
Fe
3+
+ H
2
Fe
2+
+ H
+
23
Standard cell potential(e.m.f),
Standard condition 298K, 1 atm
and/or 1 M

sel
E
=
anode cathode
E E =

sel
E
Ox d
E E + =
Re

sel
E
24
E.g:: Sel Danielle



E.g:
In
+
In
3+
+ 2e
Br
2
+ 2e 2Br
-


=1.46V. find

V E
Zn Zn
763 . 0
|
2
=
+
V E
Cu Cu
337 . 0
|
2
+ =
+

sel
E

Ox
E
25
Nernst Equation







R = gas constant, 8.314 Jmol-1K-1
T = Absolute temperature (K)
z = numbers of mole electron involved in
overall reaction.
F = 96500 C mole
-1
Q = reaction quotient
Q < K then the reaction is proceeding in the forward direction.
Q > K then the reaction is proceeding in the reverse direction.

Q ln
zF
RT
E E
sel sel
=

sel
E

sel
E
= Standard cell potential
= Cell potential
26
Nernst Equation
Equilibrium :
E
sel
=0 and Q = K
K
nF
RT
E
sel
ln 0 =

sel
E
K
nF
RT
ln =
27
] [
] [
ln
reduction
oxidation
a
a
nF
RT
E E
sel sel
=

28
The liquid junction potential,E
J

Potential difference across the
interface of two electrolytes or
between difference concentration of
electrolytes

Slower the diffusion of faster ions
After the brief period of times, the
ions diffuse at the same rate.
29
E
j
= E
w/t
- E
w/o


) (
) (
ln ) 2 1 (
1
2
m a
m a
zF
RT
t E
j

+
=
30
Electrochemical thermodynamic



Standard
sel
nFE G = A

=
sel sel
E E

A = A G G

= A
sel
nFE G
31
Entropy change
P P
T
E
nF
T
G
S
|
.
|

\
|
c
c
=
|
.
|

\
|
c
A c
= A
S T G H A + A = A
P
T
E
nFT nFE H
|
.
|

\
|
c
c
+ = A
Gibbs-helmholtz.
32
vant Hoff isotherm
] reactant a [
] product a [
ln
nF
RT
E E
sel sel
=

sel
nFE G = A

= A
sel
nFE G
] reactant [
] product [
ln
a
a
nF
RT
nF
G
nF
G

A
=
A

33
) reactant (
) product (
ln
a
a
RT G G + A = A

vant Hoff isotherm