Electrochemical Cells

ELECTROCHEMICAL CELLS
1
A device in which a reaction occurs with the
production of an electrical potential difference
between 2 electrodes
Cell single arrangement of 2 electrodes
Battery combination of 2 or more cells
connected in series or in parallel
2
ELECTROLYTIC CELL VS
ELECTROCHEMICAL CELL
3
Electrochemical Cells Electrolytic Cells
Converts chemical energy into
electrical energy
Converts electrical energy into
chemical energy.
Redox reaction is spontaneous
and is responsible for the
production of electrical energy
Redox reaction is not spontaneous
and electrical energy has to be
supplied to initiate the reaction
2 half cells in different containers
connected with a salt bridge
2 electrodes in the same container
Anode is negative and cathode is
positive electrode
Anode is positive and cathode is
negative electrode
The electrons are supplied by the
species getting oxidized. They
move from anode to the cathode
in the external circuit
The external battery supplies the
electrons. They enter through the
cathode and come out through the
anode
4
ELECTROLYTIC CELL VS
ELECTROCHEMICAL CELL
Consists of 2 half cells
Each half-cell consists of an electrode, and an
electrolyte
The two half-cells may use the same electrolyte,
or they may use different electrolytes
The chemical reactions in the cell may involve
the electrolyte, the electrodes or an external
substance
5
one half-cell lose electrons (OXIDATION) to their
electrode while species from the other half-cell
gain electrons (REDUCTION) from their electrode
A salt bridge is often employed to provide ionic
contact between two half-cells with different
electrolytes
to prevent the solutions from mixing and causing
unwanted side reactions.
allows the flow of ions to maintain a balance in charge
between the oxidation and reduction vessel
6
Salt Bridge
Contains an inert electrolyte solution such as KCl
or NH
4
NO
3
, whose ions will not react with the
ions in solution or with the electrodes
In solution
the cations (Zn
+2
, Cu
+2
, and K
+
) move toward the
cathode
The anions (SO
4
-2
and Cl
-
) move toward the
anode
7
DANIELL CELL
DANIELL CELL
8
Anode: Oxidation
Zn metal dissolves, decrease in mass
of zinc electrode
Zn(s) Zn
+2
+2e
-
Cathode: Reduction
Cu
+2
+ 2e- Cu(s)
Cu is deposited on the cathode
Flow of electrons is from Zn to
Cu electrode (Zn more readily
losses electrons than Cu.
Net Reaction: Zn(s) + Cu
+2
Zn
+2
+ Cu(s)
9
As a zinc atom provides the electrons,
it becomes a positive ion and goes
into aqueous solution, decreasing the
mass of the zinc electrode
Zn(s) Zn
2+
(aq) + 2e
-
oxidation

On the copper side, the two electrons
received allow it to convert a copper
ion from solution into an uncharged
copper atom which deposits on the
copper electrode, increasing its mass
Cu
2+
(aq) + 2e- Cu(s) reduction
10
An electrical current flows from
the anode to the cathode
because of the difference in
electrical potential energy
between the electrodes which is
measured by the voltmeter
Cell voltage
EMF
Cell potential
11
Cell voltage is dependent on
Nature of electrodes and ions
Concentration of ions
Temperature at which the cell is
operated
12
Representation of the cell
Zn(s)/Zn
+2
//Cu
+2
/Cu(s)
Zn(s)/Zn
+2
(1M)//Cu
+2
(1M)/Cu(s)
The emf of a single cell is
impossible to measure

H
2
electrode: reference electrode
SHE- Standard Hydrogen Electrode
Pt electrode: provides a surface on which H
2

dissociates
13
HOW TO DETERMINE THE STANDARD
REDUCTION POTENTIAL (SINGLE CELL)
Cathode: 2H
+
(1M) + 2e

H
2
(1atm) E
o
= 0V
Anode: Zn(s) Zn
+2
+ 2e

_______________________________________________________________

Zn(s) + 2H
+
(1M) Zn
+2
+ H
2
(1atm) E
o
= 0.76V

Cell diagram: Zn(s)/Zn
+2
(1M)//H
+
(1M)/H
2
(1atm)/Pt(s)
Anode: H
2
(1atm) 2H
+
(1M) + 2e

E
o
= 0V
Cathode: Cu
+2
+ 2e

Cu(s)
________________________________________________________________
H
2
(1atm)
+
Cu
+2
2H
+
(1M) + Cu(s) E
o
= 0.34V

Cell diagram: Pt(s)/H
2
(1atm)/H
+
(1M)//Cu
+2
(1M)/Cu(s)
16
17
o
anode
o
cathode
o
cell
E E E =
Zn Zn H H
o
cell
E E E
/ /
2
2
+ +
=
Zn Zn
E
/
2
0 76 . 0
+
=
0 34 . 0
) ( /
2
=
+
s Cu Cu
E
2
2
/ / H H Cu Cu
o
cell
E E E
+ +
=
Combining the 2 electrodes:
) ( / // / , , / // / ) (
2
2 2
2
s Cu Cu H H Pt Pt H H Zn s Zn
+ + + +
V E
cell
10 . 1 ) 76 . 0 ( 34 . 0 = =
Standard Ag-AgCl electrode
Ag is in contact with AgCl(s) which is a highly
insoluble salt
The whole assembly is immersed in a KCl solution
where Cl
-
is 1m
Ag/AgCl/Cl
-
With Hydrogen electrode:
Pt/H
2
/H
+
//Cl
-
/Agcl(s)/Ag
18
OTHER STANDARD ELECTRODES
Standard Ag-AgCl electrode
Half Reactions

19
+
+ e H H
2
2
1

+ + Cl Ag e AgCl
+
+ + + Cl Ag H AgCl H
2
2
1
Calomel Electrode
Hg is in contact with mercurous chloride, immersed
in a 0.1m solution of KCl or in a standard solution of
KCl
With hydrogen electrode:
Pt/H
2
/H
+
(1m)//Cl
-
(0.1m)/Hg
2
Cl
2
(s)/Hg

20
Calomel Electrode
Half Reactions

21
+
+ e H H
2
2
1

+ + + Cl Hg Cl Hg e
2 2
2
1
+
+ + + H Cl Hg Cl Hg H
2 2
2
1
2
2
1
For potentials of Calomel Electrodes, refer to Table 14-2
(Maron and Lando)
Glass Electrode
consists of a long glass tube with a thin walled glass bulb at
one end
Special glass (Corning glass containing 22% Na
2
O, 6% CaO and
72%SiO
2
) of low melting point and high electrical conductance
is used for the purpose.
The glass can specifically sense hydrogen ions up to a pH of
about 9.
The bulb contains 0.1 M HCl and a Ag/AgCl electrode (as
internal reference electrode), is immersed into the solution
and connected by a platinum wire for electrical contact.
The electrode is represented as,
Ag | AgCl (s) | HCl (0.1M) | glass
22
Gas Electrode
consists of a gas bubbling about an inert metal wire or foil
immersed in a solution containing ions to which the gas is
reversible
Metal Wire is usually platinized platinum
To facilitate equilibrium between the gas and its ions
Serve as electric contact for the electrode
Examples:
Hydrogen electrode which is reversible to hydrogen ions
Chlorine electrode which is reversible to chloride ions
Oxygen electrode whose emf depends on the activity of hydroxyl
ions
23
Gas Electrode
Hydrogen electrode
24
( ) ( )
+
+ =
+
e a H P g H
H
H
2
,
2 2
1
2 / 1
2
2 2
ln
H
H
o
H H
P
a
F
RT +
= c c
2 / 1
2
2
ln
H
H
H
P
a
F
RT +
= c
Gas Electrode
Chlorine electrode
25
( ) ( )

= +
Cl
Cl
a Cl e P g Cl
2
,
2 2
1
2 / 1
2
2 2
ln
Cl
Cl
o
Cl Cl
P
a
F
RT
= c c
The E
o
values apply to half cell reaction as read in the
forward direction
Under standard condition, any species on the left of a
given half cell reaction will react spontaneously with a
species that appear on the right of any half cell reaction
(diagonal rule)
(Based on Table 14-3, Maron and Lando) The more
positive the value of E
o
is, the greater the tendency for
the substance to be oxidized

26
STANDARD ELECTRODE POTENTIAL
Half cell reaction is reversible. Depending on conditions,
any electrode can act as either an anode or cathode.
Changing the stoichiometric coefficient of a half cell
reaction does not affect the value of E
o
.

27
For the Zn-Cu electrodes, the emf varies with activities
of the Zn
+2
and Cu
+2
ions in the 2 solutions
When Zn
+2
is large the tendency for the reaction:
Zn(s) Zn
+2
+ 2e- to occur decreases
When Cu
+2
increases, the tendency of
Cu
+2
+ 2e- Cu(s) to occur increases

28
1. Any cell reaction is the sum of the single electrode
reactions as they occur in the cell.
2. The total cell emf is the algebraic sum of the single
electrode potentials provided each emf is affixed with
sign corresponding to the reaction as it actually takes
place at the electrode.

29
Rules on Cell Reactions and
emf
3. If any of the cell is written down with the negative
electrode on the left, so that the electrons flow through
the external circuit from left to right, the cell reaction
deduced by rule 2 for the cell is positive
4. If the wrong assumption be made with respect to
the polarity of the electrodes, rule 3 will yield a
negative emf corresponding to the non-
spontaneous reaction. To obtain the spontaneous
reaction and its emf, reverse the reaction and
change the sign of the emf without changing the
magnitude.
30
Rules on Cell Reactions and
emf
THERMODYNAMICS OF
31
For the reaction:
... ... + + = + + dD cC bB A o
...
...
ln
b
B A
d
D
c
C
o
a a
a a
RT G G
o
+ A = A
(
+ =
b
B A
d
D
c
C
o
a a
a a
RT nF nF
o
c c ln
a
o
b
B A
d
D
c
C
o
k
nF
RT
a a
a a
nF
RT
ln ln =
(
= c c c
o
THERMODYNAMICS OF
32
For the zinc electrode:
Zn
Zn
o
Zn Zn
a
a
nF
RT +
=
2
ln c c
( ) a Zn Zn
+ 2
/
( )
+
+ = e a Zn s Zn 2 ) (
2
oxidation
Since zinc is solid, 1 =
Zn
a
+
=
2
ln
Zn
o
Zn Zn
a
nF
RT
c c
THERMODYNAMICS OF
33
For the zinc copper assembly:
( ) ) ( / // /
2 2
2
s Cu Cu a Zn Zn
Zn
+ +
+
( )
+
+ = e a Zn s Zn 2 ) (
2
oxidation
( )
+ + + +
+ =
2 2 2 2
ln
2
Cu Zn
o
Cu
o
Zn
a a
F
RT
c c c
( ) ( ) ) ( 2
2 2
2 2
s Cu a Zn e a Cu
Zn Cu
+ = +
+ +
+ +
( ) ) ( 2
2
2
s Cu e a Cu
Cu
= +
+
+
reduction
Chemical Cells the driving force is chemical reaction
between electrodes and solute ions
Cell without Transference
Cell with Transference
Concentration Cells the driving force is a dilution
process. Changes in concentration can occur either in the
electrolyte or at the electrode.
Cell without Transference
Cell with Transference

34
TYPES OF ELECTROCHEMICAL CELLS
Chemical Cells without Transference
No liquid junction
One of the electrodes is reversible to the cation, the other
to the anion of the electrolyte.
Example:

Electrolyte: HCl
H
2
is reversible to H
+
(from HCl)
AgCl is reversible to Cl
-
(from HCl)

35
Ag s AgCl a HCl P g H
HCl H
/ ) ( ), ( / ) , (
2
2
TYPES OF ELECTROCHEMICAL
CELLS
36
HCl H
/ ) ( ), ( / ) , (
2
2
( )
2
1
2
2 2
+
+ e H H

+ + Cl s Ag e s AgCl ) ( ) (
+
+ + + Cl s Ag H s AgCl H ) ( ) (
2 2
1
0 =
o
c
2225 . 0 =
o
c
2225 . 0 =
o
c
Example

CELLS
37
Example

HCl H
/ ) ( ), ( / ) , (
2
2
2
1
2
2
1
2
ln ln
H
HCl
o
AgCl Ag
H
Cl H
o
AgCl Ag cell
P
a
F
RT
P
a a
F
RT
= =

+
c c c
When
atm P
H
1
2
=
( ) ( ) + = =
Cl H
o
AgCl Ag HCl
o
AgCl Ag cell
m m
F
RT
a
F
RT
c c c ln ln
c c c m
F
RT
m
F
RT
o
AgCl Ag
o
AgCl Ag cell
ln
2
ln
2 2
= =

+
+ + + Cl s Ag H s AgCl H ) ( ) (
2 2
1
CELLS
38
Example

HCl H
/ ) ( ), ( / ) , (
2
2
c c ln ln
2
F
RT
m
F
RT
o
AgCl Ag cell
= +

m
F
RT
cell
ln
2
+ c
m or
o
AgCl Ag
c
Chemical Cells with Transference
There is boundary between the two solutions of different
electrolytes.
Not considered suitable for exact evaluation of the
thermodynamic properties of the cell:
Under suitable experimental conditions, the cell may be
used for the determination of pH.
Examples:

39
) ( / // / ) (
2 2
s Cu Cu Zn s Zn
+ +
) ( / // ) 1 ( ), ( /
2
2 2
s Cu Cu N KCl s Cl Hg Hg
+
Contact between 2 solutions of different concentrations
or different ions or both lead to a JUNCTION POTENTIAL
Ions diffuse across the boundary from the side of higher
to one of lower concentration
Velocities of ions are different causing a separation of
charges resulting in a junction potential

40
j cell
c c c c + + =
2 1
Contact between 2 solutions of different concentrations
or different ions or both lead to a JUNCTION POTENTIAL
A salt bridge eliminates completely the junction potential
When c
j
is disregarded, it is customary to write 2 vertical
lines between solutions:

41
) ( / // / ) (
2 2
s Cu Cu Zn s Zn
+ +
It is characteristic of a chemical cell that they involve in
their emf equation the ACTIVITIES of ions rather than the
mean activities of the electrolytes as a whole.
Example

42
) ( / ) ( // ) ( / ) (
2 4 1 2
s Cd m CdSO m ZnCl s Zn
CELLS
43

) ( / ) 1 . 0 ( // ) 5 . 0 ( / ) (
4 2
s Cd m CdSO m ZnCl s Zn = =
+
+ e Zn Zn 2
2
Cd e Cd +
+
2
2
Cd Zn Cd Zn + +
+ + 2 2
7618 . 0 =
o
c
403 . 0 =
o
c
3588 . 0 =
o
c
CELLS
44

) ( / ) 1 . 0 ( // ) 5 . 0 ( / ) (
4 2
s Cd m CdSO m ZnCl s Zn = =
2
2
2
2
2
2
ln
2
ln
2
+
+
+
+
+
+
= =
Cd
Zn
Cd
Zn
o
Cd
Zn
o
m
m
F
RT
a
a
F
RT
c c c
Concentration Cells without Transference
Emf is due to transfer of material from one electrode to
another due to concentration difference
Example
2 hydrogen electrodes in the same solution of unequal
pressures

45
) ( / / ) (
2 2 1 2
P H H P H
+ No liquid junction
No Transference
Concentration Cells
Emf is due to transfer of material from one electrode to
another due to concentration difference
Example
2 amalgam electrodes of different concentrations dipped
in a solution of metal ion

46
) )( ( / / ) )( (
2
2
1
C C Hg Cd Cd C C Hg Cd
Cd Cd
= =
+
CELLS
47
Electrode Concentration Cells without Transference
2 like electrodes at different concentrations but
electrolyte is the same for both

( ) ) ( / / ) (
2 2 1 2
2 2
P P H a H P P H
H
H
H
= =
+
+
( )
+
+ =
+
e a H P H
H
) (
1 2 2
1
( ) ) (
2 2 2
1
P H e a H
H
= +
+
+
) ( ) (
2 2 2
1
1 2 2
1
P H P H =
2
1
1
1
ln
P
a
F
RT
H
+
= c
+
=
H
a
P
F
RT
2
1
2
2
ln c
1
2
1
2
2 1
ln
2
ln
2
1
2
1
P
P
F
RT
P
P
F
RT
= = +c c
c
o
= 0 for concentration cells
CELLS
48
Electrode Concentration Cells without Transference
2 like electrodes at different concentrations but
electrolyte is the same for both

( ) ( ) ( )
2
2
1
) ( / / ) (
2
a a Hg Zn a Zn a a Hg Zn
Zn
zn
Zn
= =
+
+
( ) ( )
+
+ =
+
e a Zn a Hg Zn
Zn
2 ) (
2
2
1
( ) ( )
2
2
) ( 2
2
a Hg Zn e a Zn
Zn
= +
+
+
( ) ( )
2 1
) ( ) ( a Hg Zn a Hg Zn =
1
1
2
ln
2 a
a
F
RT
Zn
+
= c
2
2
2
ln
2
+
=
Zn
a
a
F
RT
c
|
|
.
|
\
|
= +
+2
2
2 1
ln
2
Zn
a
a
F
RT
c c
CELLS
49
Electrolyte Concentration Cells without Transference

( ) Ag s AgCl a HCl atm g H / ) ( , / ) 1 , (
1 2
( ) ( )

+ = + Cl s Ag e s AgCl
1 1
ln a
F
RT
o
= c c
+
+ = e H atm g H ) 1 , (
2 2
1
( )
1 2 2
1
) ( ) ( ) 1 , ( a HCl s Ag s AgCl atm g H + = +
CELLS
50

2 2
( ) ( )

+ = + Cl s Ag e s AgCl
+
+ = e H atm g H ) 1 , (
2 2
1
( )
2 2 2
1
) ( ) ( ) 1 , ( a HCl s Ag s AgCl atm g H + = +
2 1
ln a
F
RT
o
= c c
CELLS
51

2 2
1 2
Combining the 2 cells, the overall reaction is
( ) ( )
2 1
2 2
1
2 2
1
) ( ) (
) ( ) 1 , ( ) ( ) 1 , (
a HCl s Ag a HCl s Ag
s AgCl atm g H s AgCl atm g H
+ =
+
( ) ( )
1 2
a HCl a HCl =
2
1
2 1
ln
a
a
F
RT
= = c c c
CELLS
52
Concentration Cells without Transference can be
assembled from chemical cells without transference
Can be used to measure the activity coefficient of an
electrolyte
Concentration of 1 electrolyte is constant, then measure the
emf of the cells with varying concentration of the second
solution

1 1
2 2
2
2
2
2
2
1
2
1
2
1
ln
2
ln ln
c
m
m
F
RT
m
m
F
RT
a
a
F
RT
cell
= = =
|
|
.
|
\
|
+ =
1
2
1
2
ln ln
2
c
m
m
F
RT
cell
CELLS
53
Concentration Cells with Transference
Electrodes are reversible to the cation

( ) ( ) ) 1 , ( / / / ) 1 , (
2 2 1 2
atm g H a HCl a HCl atm g H
+
+ = e a H H ) (
1 2 2
1
2 2
1
2
) ( H e a H = +
+
) ( ) (
1 2
a H a H
+ +
=
CELLS
54

( ) ( ) ) 1 , ( / / / ) 1 , (
2 2 1 2
) ( ) (
1 2
a Cl t a Cl t

=
) ( ) 1 ( ) ( ) 1 (
2 1
a H t a H t
+
=
) ( ) (
1 2
a HCl t a HCl t

=
Cl
-
ions move from RL
H
+
ions move from LR
) ( ) (
1 2
a H a H
+ +
=
CELLS
55

( ) ( ) ) 1 , ( / / / ) 1 , (
2 2 1 2
1
2
2
1
2
1
ln ln ln
a
a
t
F
RT
a
a
t
F
RT
a
a
F
RT
t
t
cell
= = =

c
(
+ = =

1
2
1
2
2
1
2
1
2
2
2
2
ln ln ) 2 ( ln ) (
c
m
m
F
RT
t
m
m
F
RT
t
cell
For transfer of material to be spontaneous
1 2
a a )
CELLS
56
Electrodes are reversible to the anion

( ) ( ) ( ) Ag s AgCl a HCl a HCl s AgCl Ag / ) ( , / , /
2 1

+ = + e s AgCl a Cl s Ag ) ( ) ( ) (
1
) ( ) ( ) (
2
a Cl s Ag e s AgCl

+ = +
) ( ) (
2 1
a Cl a Cl

=
CELLS
57

2 1
) ( ) (
2 1
a Cl a Cl

=
) ( ) (
2 1
a H t a H t
+
+
+
+
=
) ( ) 1 ( ) ( ) 1 (
1 2
a Cl t a Cl t

+
+
=
) ( ) (
2 1
a HCl t a HCl t
+ +
=
CELLS
58

2 1
2
1
1
2
1
2
ln
2
ln ln
a
a
t
F
RT
a
a
t
F
RT
a
a
F
RT
t
t
cell + +
= = =
+
+
c
(
+ = =
+ +
2
1
2
1
2
2
2
2
2
1
2
1
ln ln ) 2 ( ln ) (
c
m
m
F
RT
t
m
m
F
RT
t
cell
For transfer of material to be spontaneous
2 1
a a )
CELLS
59
The Junction Potential (electrodes reversible to the
cation)
) ( ) (
1 2
a H a H
+ +
=
( ) ( ) ) 1 , ( / / / ) 1 , (
2 2 1 2
Sum of 2 electrode potential
( )
( )
2
1
2 1
ln
+
+
= + =
H
H
a
a
F
RT
c c c
( )
( )
2
1
ln
+ +
+ +
=
H H
H H
m
m
F
RT
c
CELLS
60
cation)
j
c c c c + + =
2 1
( )
2 1
c c c c + =
j
1 1
2 2
1 1
2 2
ln ln ) 2 (
c
m
m
F
RT
m
m
F
RT
t
j

(
=

( )
(
=

1 1
2 2
ln 1 2
c
m
m
F
RT
t
j
( )
(
=
+
1 1
2 2
ln
c
m
m
F
RT
t t
j
CELLS
61
anion)
( )
(
=
+
2 2
1 1
ln 1 2
c
m
m
F
RT
t
j
( )
(
=
+
2 2
1 1
ln
c
m
m
F
RT
t t
j
SOLUBILITY PRODUCT AND EMF
62
Difficultly soluble salt: AgBr(s)
Find 2 electrodes whose reactions lead to the
overall process

+
= a a K
s
: / electrode Ag Ag
+
: , /

Br AgBr Ag
+
+ = e Ag s Ag ) (

+ = + Br s Ag e s AgBr ) ( ) (
+
+ = Br Ag s AgBr ) (
7991 . 0 =
o
c
711 . 0 =
o
c
v
o
728 . 0 = c
SOLUBILITY PRODUCT AND EMF
63
Difficultly soluble salt: AgBr(s)
Find 2 electrodes whose reactions lead to the
overall process

+
= a a K
s
s
o
k
nF
RT
ln = c
s
k ln
) 490 , 96 )( 1 (
) 298 )( 314 . 8 (
7280 . 0 =
13
10 86 . 4

= x k
s
Cell is assembled in which one of the electrodes is
reversible to the hydrogen ions
Dipped into the solution whose pH is to be
determined
The other electrode is usually a calomel
Either with salt bridge or reference electrode is
immersed directly into the solution
emf is measured with a potentiometer

64
POTENTIOMETRIC DETERMINATION
OF PH
POTENTIOMETRIC DETERMINATION
OF PH
65
Hydrogen Electrode
2
1
2 2
ln ln
H
H
H
P
F
RT
a
F
RT
+ =
+
c
+
=
H
a pH log
2
1
2 2
log
3026 . 2
log
3026 . 2
H
H
H
P
F
RT
a
F
RT
+ =
+
c
2
1
2 2
ln
3026 . 2 3026 . 2
H H
P
F
RT
pH
F
RT
+ = c
when
atm P
H
1
2
=
pH
F
RT
H
3026 . 2
2
= c
LEAD STORAGE CELL
66
LEAD STORAGE CELL
67
LEAD STORAGE CELL
68

+ + e PbSO aq SO s Pb 2 ) ( ) (
4
2
4
) ( 2 ) ( 2 ) ( ) ( 4 ) (
2 4
2
4 2
l O H s PbSO e aq SO aq H s PbO + + + +
+
) ( 2 ) ( 2 ) ( 2 ) ( 4 ) ( ) (
2 4
2
4 2
l O H s PbSO aq SO aq H s PbO s Pb + + + +
+
LEAD STORAGE CELL
69
Recharging
Reaction is reversed by applying an external voltage at the
cathode and anode
Degree to which the battery is discharged can be checked
from the density of the electrolyte (H
2
SO
4
)
For fully charged battery, =1.2 g/ml
emf decreases with decreasing temperature (1.5v x 10
-
4
/
o
C)
Real cause of breakdown: increase in viscosity of the
electrolyte as T decreases

Electrochemical Cells

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