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ELECTROCHEMICAL CELLS

CHAPTER III
Electrochemical cells may be used to perform 2 functions: (a) to convert
chemical energy into electrical, and (b) to convert electrical energy into
chemical.
Examples for (a) dry cell and lead storage battery (b) charging battery,
accumulator, electrolytic purification of copper.
Dry cell battery
Lead acid battery
accumulator
charging battery
electrolytic purification of copper
Reversible and Irreversible Cells
The reversibility of a cell deals with thermodynamic principles of cell energy.
Thermodynamic reversibility conditions for a cell are:
a. The driving force and opposing forces be only infinitesimally different from each
other,
b. It is possible to reverse any change taking place by applying a force
infinitesimally greater than the one acting.
For a reversible cell, the potential difference measured under appropriate
conditions may be substituted into relevant thermodynamic relations.
When this conditions are not satisfied, the cell is said to be irreversible.
Example for reversible cell: A cell composed of Zn and Ag/AgCl electrodes in
ZnCl electrolyte solution. When potential is supplied to the cell, the electrons
flow from Zn to Ag/AgCl electrodes, and the net reaction is
Zn(s) + AgCl(s) Ag(s) + Zn
2+
+ Cl
-
This process continues as long as the external opposing potential is
infinitesimally smaller than that of the cell. However as soon as the potential
becomes slightly larger, the direction of the cell is reversed and so is the cell
reaction.
Example of irreversible cell: A cell composed of two Pt electrodes immersed in
H
2
SO
4
. When the 2 electrodes are short-circuited, no current flows and no
reaction takes place because the electrodes are identical. However when the
cell is connected with potential then H
2
is evolved at one electrode and O
2
at
the other

Electromotive Force
The difference of potential which causes a current to flow from electrode
of higher potential to the one of lower is called the electromotive force of
a cell (emf). The unit is volt.
Potentiometer equipped with a galvanometer is used to measure precise
emf of a cell (to 10
-7
Volt) instead of a voltmeter. Voltmeter draws some
current from the cell, causing thereby a change in the emf due to
formation of reaction products at the electrodes and changes in the
concentration of the electrolyte around the electrodes.
Poggendorf Potentiometer
galvanometer
voltmeter
Standard Cells
It is essential to have available as standard cells whose potentials are
reproducible, constant with time, and well known. Also such cells should
be reversible, should not be subject to permanent damage due to passage
of current through them, and should preferably have low temperature
coefficients of emf. These cells that most closely approximate these
properties are Weston unsaturated and saturated cells.
Its potential at any temperature (
o
C) in volt:
c
t
= 1.01830 4.06x10
-5
(t-20)-9.5x10
-7
(t-20)
2
3.1. Cell Voltages and currents
The simplest electrochemical unit consists of
an ionic conductor sandwiched between two
electronic conductors.



This sandwich combination of any ionic
conductor and any pair of (similar or
dissimilar) electronic conductors constitutes
an electrochemical cell.
Electronic
conductor
Ionic
conductor
Electronic
conductor
electrode electrode
The measured potential difference of the left electronic conductor
with respect to the right will be denoted as AE, the cell voltage. The
value may be positive, negative, or zero.
It is possible for electricity to cross the interface between an
electronic and an ionic conductor only by virtue of an
electrochemical reaction occurring there. The site of this reaction,
the interfacial junction, is known as electrode.
The reaction that occurs at the right electrode produces electrons is
called oxidation. The electrode is called the anode. At the left hand
electrode, electrons are consumed, signifying a reduction, the
electrodes name is cathode.
The two electrode reactions complete the circuit and permit
electricity to flow through the load. Energy is delivered by the cell
into the load. A cell which provides energy in this way is called a
galvanic cell.
left
electronic
conductor
Ionic
conductor
right
electronic
conductor
V
red black
AE
PbO
2
H
2
O H
+
HSO
4
-

Pb

V
red black
PbSO
4
PbSO
4

e-
2 V
Lead/acid cell
Galvanic Cell (ex: lead/acid cell)
PbO
2
H
2
O H
+
HSO
4
-

Pb

V
red black
PbSO
4
PbSO
4

e-
e-
e-
e-
load
AE=1.8 V
Pb
(s)
+ HSO
4
-
(aq)
2e
-
+ PbSO
4(s)
+H
+
(aq)
2e
-
+ PbO
2(s)
+ HSO
4
-
(aq)
+3H
+
(aq)
PbSO
4(s)
+ 2H
2
O(l)

A complete circuit
Electrons flow through the load from right to left but because electrons are negatively
charged, we speak of electricity or current flowing from left to right through the load.
When current flows, the galvanic cell shows the decreasing in the voltage. The decreasing in
voltage magnitude occurs when energy is taken from the galvanic cell. The phenomenon is
called polarization and the effect becomes greater if the current is increased. (1.8 V < 2 V)
Electrolytic Cell
PbO
2
H
2
O H
+


HSO
4
-

Pb

V
red black
PbSO
4
PbSO
4

e-
e-
e-
e-
load
AE=2.1 V
2e
-
+ PbSO
4(s)
+H
+
(aq)
Pb
(s)
+ HSO
4
-
(aq)
PbSO
4(s)
+ 2H
2
O(l) 2e
-
+ PbO
2(s)
+ HSO
4
-
(aq)
+3H
+
(aq)
dc voltage
source 2.4 V
+ -
A
The electric current can be made to flow in the opposite direction through the lead/acid
cell by using an external source to drive electrons from the PbO
2
through the load to the
Pb. This external source could be another battery, a cars generator, a battery charger or a
variable-voltage DC voltage source as shown below. This cell is called an electrolytic cell.
In electrolytic cell, polarization always leads to a voltage greater in magnitude than that in
the absence of current flow (2.1 V > 2 V)
Null Voltage:
equilibrium cell voltage/reversible cell voltage/null
voltage/rest voltage/open-circuit voltage/AE
n

150

100

50

0

50

100

150
_

_

_

_

_

_

_
d
i
s
c
h
a
r
g
i
n
g

c
u
r
r
e
n
t
/
m
A

c
h
a
r
g
i
n
g

c
u
r
r
e
n
t
/
m
A

1.4 1.6 1.8 2.0 2.2 2.4
null
voltage
voltage of PbO
2

electrode vs Pb
electrode/ V
Voltammogram
(Volt-ampere plot)
Null voltage: a voltage value where there is a perfect balance between the applied and
cell voltage, so that no current flows.
Definition:
Null voltage: a voltage value where there is a
perfect balance between the applied and cell
voltage, so that no current flows.
Equilibrium cell voltage: a voltage at which the
balance exists.
Reversible cell voltage: because a minute change
in the applied voltage could cause a current flow
to reverse direction.
Rest voltage: because no current flows
Open circuit voltage. Since no current flows, it
makes no difference if the circuit is interrupted,
as by opening the switch.
Equilibrium Cell
PbO
2
H
2
O H
+

HSO
4
-

Pb

V
red black
PbSO
4
PbSO
4

I = 0
load
AE=2 V
PbSO
4(s)
+H
+
(aq)
Pb
(s)
+ HSO
4
-
(aq)
PbO
2(s)
+ HSO
4
-
(aq)
+3H
+
(aq)
PbSO
4(s)
+ 2H
2
O(l)

dc voltage
source 2.4 V
+ -
A
2e
-

2e
-

A equilibrium cell is neither a galvanic nor electrolytic cell. There is no anode and
cathode, since no chemistry is occurring.
The overall chemical reaction is: AgCl
(s)
+ H
2(g)
Ag
(s)
+ H
+
(aq)
+ Cl
-
(aq)
) (
/
) ( ) (
) ( ) ( ) (
) (
~
~
Ag e
g H s AgCl
Pt e aq Cl aq H
s Ag
cell
a a a
a a a a
K K

+
= =
2 1
2
2 1
2
/
) ( ) (
) ( ) (
) (
exp
g H s AgCl
aq Cl aq H
s Ag
n
cell
a a
a a a
RT
E F
K
+
)
`

=
A
Ag

H
2
O H
+
Cl
-
30 mM HCl
Pt

V
red black
AgCl
e-
e-
e-
e-
load
H
2
AE
n
= 410.7 mV
) (
) (
~
~
exp
Pt e
Ag e
n
a
a
RT
E F

=
)
`

A
because
then
THERMODYNAMICS OF EQUILIBRIUM CELLS
= 5692 at 298 K experimental cell
Conditions for an equilibrium cell
Circumstance Cell Voltage Activities
Experimental cell
Short-circuited cell
Standard conditions
AE
n
0
AE
o
Experimental values
Adjusted
unity
K
a a
a a a
K
g H s AgCl
aq Cl aq H
s Ag
cell
= =
+
2 1
2
/
) ( ) (
) ( ) (
) (
When the activities of ions and hydrogen in the cell are adjusted so that the
cell voltage AE
n
= 0 (short-circuited cell), the chemical equilibrium will be:
The overall chemical reaction is: AgCl
(s)
+ H
2(g)
Ag
(s)
+ H
+
(aq)
+ Cl
-
(aq)
The electrochemical equilibrium constant of a cell in which a particular net
reaction occurs is identical to the chemical equilibrium constant of that
reaction.
nF
G
F
G
K
F
RT
a a
a a a
F
RT
E E
o o
g H s AgCl
aq Cl aq H
s Ag
n
o
A A
A A = = =

+ =
+
) ln( ln
/
) ( ) (
) ( ) (
) (
2 1
2
For cell reaction:
oO + pP + . qQ + rR +
The null cell voltage AE
n
is given by the relationship:
Nernsts equation:
Standard Cell
In standard states, all reactants and products of both electrode reactions are in their
standard states, and therefore all activities are unity. The potential difference that the
cell would develop under these conditions is known as the standard cell voltage and is
represented by AE
o
.

=
...
...
ln
p
P
o
O
r
R
q
Q
o
n
a a
a a
nF
RT
E E A A
Methods in determining standard cell voltage:
Experimental measurements
From the equilibrium constant K of the cell reaction:


From the Gibbs energy change accompanying the cell reaction:


From the standard electrode potentials of the left and right hand
electrodes:
{ } K
nF
RT
E
O
ln = A
nF
G G
nF
G
E
o
t reac
o
product
o
O
tan
E E
A
A

= =
o
r
o
l
o
E E E = A
Example:
3.1. From the value AE
o
= 1.923 V for the lead/acid cell, calculate the
equilibrium constant of the
2PbSO
4
(s) + 2H
2
O(l) Pb(s) + PbO
2
(s) + 2HSO
4
-
(aq) + 2H
+
(aq)
reaction.
Calculate the null potential (AE
n
) if the acid concentration is 5.2 molar.
Given: standard Gibbs energy, AG
o

PbSO
4
= -813.76 kJ/mol
H
2
O = -237.13 kJ/mol
PbO
2
= -218.96 kJ/mol

HSO
4
-
= -755.91 kJ/mol
2. For the reaction: AgCl
(s)
+ H
2(g)
Ag
(s)
+ H
+
(aq)
+ Cl
-
(aq)
, determine
the equilibrium constant and standard electrode potential, if the
standard Gibbs free energy of:
AgCl = -109.95 kJ/mol
Cl
-
= -131.02 kJ/mol
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