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MODULE-1 ELECTRODE POTENTIAL & CELLS

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Electrochemistry: It is a branch of chemistry which deals with the study of transformation of chemical
energy into electrical energy and vice versa

Electrochemical cell and Classification with examples:


An electrochemical cell is a device, which is used to convert chemical energy into electrical energy and vice
versa.
These electrochemical cells are classified into two types as follows.

1) Galvanic or Voltaic cells: These are the electrochemical cells, which convert chemical energy into electrical
energy.
Ex. Daniel cell, Dry cell, etc
2) Electrolytic cells-are devices which convert electrical energy into chemical energy.
Example: Electrolysis of molten NaCl, Recharge process of lead acid battery

Galvanic or Voltaic cells:


Galvanic or Voltaic cells are again classified into three types as follows

a) Primary cells: These are the cells which serve as a source of energy only as long as the active chemical
species are present in the cell. The cell reactions are irreversible. These are designed for only single discharge
and cannot be charged again.
Ex: Dry Cell, Zn Hgo cell, Zn-Ag2o cell etc.

b) Secondary cells: These cells are chargeable and can be used again and again. The cell reactions are
reversible and are often called as reversible cells. During discharging the cells acts like voltaic cell converting
chemical energy into electrical energy. During charging the cell acts like electrolytic cell by converting electric
energy into chemical energy, hence these batteries are called as storage battery.
Ex: Lead acid Battery, Ni-cd cells. Lithium ion cells etc.

c) Concentration of cells:
These are the electrochemical cells consisting of same metalelectrodes dipped in same metal ionic solution in
both the half cells butare different in the concentration of the metal ions.
Ex: Cu/Cu2+ (M1) || Cu2+ (M2)/Cu

Ex: Copper concentration cell, Zinc concentration cell

Oxidation: A species loses one or more electrons resulting in the increase in its oxidation number.

Reduction: A species gain one or more electrons resulting in a decreasing in its oxidation number.

Oxidation should accompanied by reduction, because if one losses electrons another must ready to accept
electrons. This reaction is called redox reaction.

Single electrode Potential:


It is defined as the potential developed at the interphase between the metal and the solution, when a
metal is dipped in a solution containing its own ions. It is represented as E

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Standard reduction potential (Eo) :
It is defined as potential developed at the interface between the metal and the solution, when a metal is dipped
in a solution containing its own ions of unit concentration at 298K. [If the electrodes involve gases then it is one
atmospheric pressure] It is denoted as E0.

Electromotive force (EMF):


It is defined as the potential difference between the two electrodes of a galvanic cell which causes the flow of
current from an electrode with higher reduction potential to the electrode with lower reduction potential.
It is denoted as E cell.
E cell = E right E left.
E cell = E cathode E anode.

Electrochemical series:
The arrangement of elements in the order of their standard reduction potential is reffered to as emf or
electrochemical series. Such a arrangement of few elements given in the table.

Mn+/M Eo (volts) Mn+/M Eo (volts)


Li+/Li -3.05 H+/H2 0.00
K+/K -2.93 Sn4+/ Sn2+ +0.15
Mg+/Mg -2.37 Cu2+/Cu +0.16
Al3+/Al -1.66 Cu+/Cu +0.52
Zn2+/Zn -0.76 I2/I- +0.54
Cr3+/Cr -0.74 Fe3+/Fe2+ +0.77
Fe2+/Fe -0.44 Hg2+/Hg+ +0.79
Cr3+/Cr2+ -0.41 Ag+/Ag +0.80
Cd2+/Cd -0.40 Hg2+/Hg +0.85
Ni2+/Ni -0.25 Pt2+/Pt +1.20
Sn2+/Sn -0.14 Cr7+/Cr3+ +1.31
Pb2+/Pb -0.13 Cl2/2Cl- +1.36
Fe3+/Fe2+ -0.041 Au3+/Au +1.50

1) A negative value indicates oxidation tendency and a positive value indicates reduction tendency with respect
to hydrogen.
2) The metal with lower electrode potential is more reactive and as the electrode potential increases, the
reactivity decreases, and metals with higher electrode potentials are nobler.
3) Metals with lower electrode potentials have the tendency to replace metals with higher electrode potential
from their solutions for example, Zn displaces Cu, and Cu displaces Ag
4) Metals with negative electrode potentials can liberate hydrogen from acidic solutions

Derivation of Nernst Equation for Electrode potential:

In 1889 Nernst derived a quantitative relationship between the electrode potential and the concentrations of
metal ions are involved. The maximum work available from a reversible chemical process is equal to the
maximum amount of electrical energy that can be obtained; it shows decrease in free energy.

Wmax = G------------------------------------[1]

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And
Wmax = difference in potential between two electrode x total quantity of charge flowing through the cell

Total quantity of charge flowing through the cell = (No. of moles of electrons) x (Faradays constant)

So Wmax = nFEcell -----------------------------[2]


equate eqn [1] & [2]
G - nFE - - - - - [3]
under std.condition, G 0 - nFE 0
consider a reversible electrode reaction,
M n ne - M
for the above reaction , equlibrium constant K can be written as
c
[M ]
K [4]
c
[M n ]
K , G and G 0 are related by a ' vant hoff reaction isotherm' ,
c
G G0 RT ln K [5]
c
substitute the values of K , G and G 0 to the above equation,
c
[M ]
- nFE -nFE0 RT ln
[M n ]
divide both the sides by - nF
RT [M ]
E E0 RT ln
nF [M n ]
under standard condition, [M ] 1

log[M n ] [6]
2.303RT
Where, E E0
nF
E = Electrode potential
E0 = standard electrode potential
n = no. of electrons
[Mn+] = Concentration of metal ions
R = Universal gas constant = 8.314J K-1 mol-1
T = Temperature (In Kelvin) = 298K

log[M n ] [7]
0.0591
E E0
cell n

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0.0591 product
E E0 log K where K c
cell 2 c reactant

E E0
0.0591
log
Species at cathode
cell 2 Species at anode
Concentrations cells:
A concentration cell is an electrochemical cell in which electrode materials and electrolytes of two half
cells are composed of same material but the concentration of two solutions are different

Ex- Cu/Cu2+(M1)|| Cu2+(M2)/Cu

A concentration cell consists of two same metal electrode dipped into their own ionic solutions of two different
concentration.

Thus in a concentration cell, the electrode with lower electrolyte concentration acts as anode and the one
with higher electrolyte concentration acts as cathode. The concentration of ions at anode increases and at
cathode decreases, when the cell is in operation.

Consider two copper rods are dipped into their own ionic solutions of M1 and M2 and it is represented as
Cu/Cu2+ (M1) Cu2+ (M2)/Cu
By electrochemical conventions, if M2 > M1 then, we have the following reactions.
At anode
2
Cu Cu ( M 1) 2e
(s)
At cathode
2
Cu ( M 2) 2e Cu
(s)
The emf of the concentration cell will be

E
0

0.0591
log M 2 E 0
0.0591
log M 1

E
cell 2 2

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0.0591 M2
E log
cell 2 M1

The emf of the cell is + ve only if M2 > M1


The following characteristics of concentration cell can be noted:
1. When M2 = M1, the concentration cell does not generate electrical energy.
2. When M2 > M1, the Ecell is + ve.
3. When M2<M1, Ecell is ve.
4. Higher the ratio of M2/M1, greater is the cell potential.

Types of electrodes:
1. Metal-Metal ion electrode: An electrode of this type consists of a metal dipped in a solution containing its
ions. Ex- Zn/Zn2+, Cu/Cu2+ etc

2. Metal-Metal salt ion electrode: These electrodes consist of a metal is in contact with a sparingly soluble salt
of the same metal dipped in a solution containing anion of the salt.

Example-Calomel (Hg|Hg2Cl2|Cl- , Silver- Silver salt electrode (Ag| AgCl |Cl-)

3. Gas electrode: Gas electrode consists of a gas bubbling about an inert metal wire, immersed in solution
containing ions to which the gas is reversible. The metal provides electrical contact and facilitates the
establishment of equilibrium between the gas and its ions.

Example-Hydrogen electrode (Pt|H2|H+) , Chlorine electrode (Pt|Cl2|Cl-)

4. Oxidation-Reduction electrode: An oxidation-reduction electrode is a one in which the electrode potential


arises from the presence of oxidized and reduced forms of the same substance in solution. The potential arises
from the tendency of one form changes into the other more stable form. The potential developed is picked up by
an inert electrode like platinum.

Example-Pt|Fe2+, Fe3+ Pt|Ce3+, Ce4+

5. Ion selective electrode: In ion selective electrode, a membrane is in contact with a solution, with which it can
exchange ions.

Example-Glass electrode.

Reference Electrodes:
Reference electrode are the electrode with reference to those, the electrode potential of any electrode
can be measured.
It can acts both as an anode or cathode depending upon the nature of other electrode.
The Reference Electrodes can be classified in to two types
i) Primary reference electrodes Ex: Standard hydrogen electrode
ii) Secondary reference electrodes Ex: Calomel and Ag/Agcl electrodes

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SHE has two main Limitations:


i) The construction of SHE is difficult. It is very difficult to maintain the concentration of H+ as 1M and
pressure H2 gas at 1atm
ii) Platinum electrode is poisoned by the impurities of the gas

Construction and working of Standard Calomel electrode (SCE):


1. Calomel electrode is a metal-metal salt Ion electrode.
2. It consists of mercury, mercurous Chloride and a solution of KCl. Mercury is placed at the bottom of a
glass tube.
3. A paste of mercury and mercurous chloride Is placed above the mercury. The space above the paste is filled
with a KCl solution of known concentration.
4. A platinum wire is kept immersed into the mercury to obtain electrical contact.
5. Calomel electrode can be represented as,
Hg | Hg2Cl2 | sat KCl

The calomel electrode can acts as anode or cathode depending on the nature of the other electrode of the cell.

Pt wire

Calomel paste

Mercury

Saturated KCl
Porous disc
The net cell reversible electrode reaction is,
Hg2Cl2(s) + 2e- 2Hg(l) + 2Cl-

Electrode potential, E E 0
2.303RT
nF

. log Cl
2

E E0
2.303RT
F

. log Cl , Where n=2


E E 0 0.0591log Cl at 298K

Therefore electrode potential of calomel electrode is depending upon the concentration of KCl.
The electrode is reversible with chloride ions.
The potential of the calomel electrode depends on the concentration of the KCl.
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For saturated KCl, the potential is 0.241V;
For 1M KCl , 0.280V;
For 0.1M KCl, 0.334V.

MEASUREMENT OF SINGLE ELECTRODE POTENTIAL USING CALOMEL ELECTRODE:


Electrode potential of a given electrode can be measured by using calomel electrode as a reference electrode.
Example-1: To measure the electrode potential of zinc: To measure the potential of the Zn- electrode, the
Zn- electrode is coupled with the SCE through a salt bridge. The anode and the cathode of the cell can be
identified by connecting the electrodes to the appropriate terminals of the voltmeter. Proper measurements can
be made only when the Zn-electrode is connected to the ve terminal and the calomel electrode to the +ve
terminal of the voltmeter indicating that Zinc electrode is anode & the calomel electrode is a cathode.
Zn ZnSO4 KCl (satd ) Hg2Cl2 Hg
Voltmeter
Pt wire
At anode: Zn Zn2+ + 2e
At cathode: Hg2Cl2 + 2e- 2Hg + 2C
Overall reaction: Zn + Hg2Cl2 Zn2+ +2Hg + 2Cl-

zinc
Ecell = Ecathode- Eanode
Electrode
=ESCE EZn2+/Zn
=0.2422V EoZn2+/Zn Calomel
EZn2+/Zn=0.2422-Ecell electrode

EZn2+/Zn=0.2422-1.001
ZnSO4
solutiom
EZn2+/Zn= - 0.76V

Example-2: To measure the electrode potential of copper: Similarly to determine the copper electrode
potential of the cell, the cell is constructed as follows. Calomel electrode being the anode is connected to ve
terminal of the voltmeter and copper electrode being the cathode is connected to the +ve terminal of the
voltmeter. Voltmeter
Hg/Hg2Cl2/KCl(sat)//Cu2+/Cu
At anode: 2Hg + 2Cl- Hg2Cl2 +2 e-

At cathode: Cu2+ + 2e Cu copper


Calomel Electrode
Overall reaction: 2Hg + 2Cl- + Cu2+ Hg2Cl2 + Cu Electrode

Ecell= Ecathode Eanode


2+
= Ecu /cu - ESCE CuSO4
Ecu2+/cu = Ecell + 0.2422 solution
Ecu2+/cu = 0.1 + 0.2422
Ecu2+/cu = +0.34V

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Advantages of calomel electrode:-

1. It is easily setup (simple to construct).


2. The cell potential is reproducible and stable over a long period.
3. It is used as a secondary reference electrode in the measurement of single electrode
potential.
4. It is the most commonly used reference electrode in all potentiometric determinations
and to measure pH of the given solution
Applications:
1. It is used as secondary reference electrode in the measurement of single electrode.
2. It is used as reference electrode in all potentiometer determinations and to measure pH of the given
solution.

Construction and working of Silver- Silver Chloride electrode:

1. Silver-Silver chloride is also a metal-metal salt ion electrode.


2. Silver and its sparingly soluble salt silver chlorides are in contact with a solution of chloride solution
ions. Generally a silver wire is coated with AgCl and dipped in a solution of KCl .
3. Cell representation is as follows

Ag |AgCl | sat KCl


Net half cell reaction is
AgCl + e- Ag + Cl-

Electrodepotential E E
0 2.303RT
nF

. log Cl , Where n=1

E E0
2.303RT
F
log Cl
E E 0 0.0591log Cl at 298K
Therefore electrode potential of calomel electrode is depending upon
the concentration of KCl.
The electrode is reversible with chloride ions.
The potential of the calomel electrode depends on the concentration of the KCl.
For 1N solution, the electrode potential is 0.223V and for saturated solution is 0.199V at 298K

Applications:

1. Used as secondary reference electrode in ion selective elctrode.


2. In determining the distribution of potential on the ship hull and pipe lines.

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Construction and working of Ion selective electrode (ISE):

Ion selective electrode is one which selectively responds to a specific ion in a mixture and the potential
developed at the electrode is a function of the concentration of that ion in the solution

Construction and working of Glass electrode:

A glass electrode is an ion selective electrode where potential depends upon the pH of the medium.

1. The glass electrode consists of a glass bulb made up of special type of glass (sodium silicate type of
glass) with high electrical conductance.
2. The glass bulb is filled with a solution of constant pH (0.1MHCl) and insert with a Ag-AgCl electrode,
which is the Internal reference electrode and also serves for the external electrical contact.
3. The electrode dipped in a solution containing H+ ions as shown in the figure.
4. The electrode representation is,
Glass | 0.1M HCl | Ag/AgCl.

GLASS
INTERNAL SOLUTION EXTERNAL SOLUTION
C1= CONSTANT MEMBRANE C2= [H+]
E1 E2

Eb
0.1 M HCl
Ag/AgCl electrode

H+ Ion Solution

GLASS ELECTRODE
The glass electrode works on the principle that when a thin glass membrane is in contact with a solution , A
boundary potential Eb is developed at layers of the glass membrane. This potential arises due to difference in the
concentration of H+ ion inside and outside the membrane.

Boundary potential, Eb = E2 E1-------------------------(1)


0 0.0591
E E . log C
1 n 1

0 0.0591
E E log C
2 n 2
Where, C1 and C2 are concentration of H+ ions inner and outer membrane.
Substitute the values of E1 & E2 into eqn (1), we get
0.0591 0.0591
Eb E 0 . log C E 0 log C
n 2 n 1

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0.0591 0.0591
Eb log C log C (n = 1)
n 2 n 1

Eb 0.0591log C 0.0591log C
2 1
(n=1, Since the concentration of the inner solution is constant, C1 is constant & (C2) = (H+))
Eb Const 0.0591log H

Where Const = K = -0.0591logC1
Eb K 0.0591 pH

The glass electrode potential is sum of the


i) Boundary potential Eb,
ii) Ag-AgCl electrode potential EAg/AgCl and
iii) Asymmetry potential Easy.

E E E E
G b Ag / AgCl asy
Theoritically, Eb = 0 for C1 = C2. However, a small additional potential is exists called Easy
potential.

E K 0.0591 pH E E
G Ag / AgCl asy

E E 0G 0.0591 pH where E 0G KE
Ag / AgCl
E
asy
G

Determination of pH using glass electrode:

pH Meter

Glass
Calomel Electrode
Electrode

Solution of
Unknown pH

Procedure: glass electrode is immersed in the solution; the pH is to be determined. It is combined with a
reference electrode such as a calomel electrode through a salt bridge. The cell assembly is represented as,

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Hg| Hg2Cl2|Cl-||Solution of unknown pH|glass|0.1M HCl|Ag|AgCl

The emf of the above cell, Ecell is measured using an electronic voltmeter with a pH meter.
The emf of the cell is given by
E E E
cell cathode anode
(1)
E E E
cell
(2)
G SCE

Since E SCE is knowing emf the cell,


E glass can be evaluated.
0
E E G 0.0591 pH . (3)
G
0
Ecell E G 0.0591 pH E
SCE
..(4)
E 0 G Ecell ESCE
pH
0.0591
Advantages
1. This electrode can be used to determine PH in the range 0-9, with special type of glass even up to 12 can be
calculated.
2. It can be used even in the case of strong oxidizing agents.
3. The equilibrium is reached quickly.
4. It is simple to operate, hence extensively used in various laboratories.

Limitations
1. The glass membrane though it is very thin, it offers high resistance. Therefore ordinary potentiometers cannot
be used; hence it is necessary to use electronic potentiometers.
2. This electrode cannot be used to determine the PH above 12

1. Two Copper electrodes placed in CuSO4 solutions of equal concentration are connected to form o
concentration cell.
a) What is the cell voltage?
b) If one of the solutions is diluted until the concentration of Cu 2+ ions is 1/5th of its original value.
What will be the cell voltage after dilution?
Solution:
a) The cell potential of concentration cell is given as
0.0591 C2
E log
cell n C1
When the concentration of the species are gqual (C2 = C1) the cell voltage is zero.
1 1
b) When one of the solution is diluted to 5 of its original value, C2 =1M & C1= 5

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0.0591 C2
E log
cell n C1
0.0591 1
E log
cell 2 1/ 5
0.0591
E log 5
cell 2
E 0.02955 0.699
cell

E 0.0206V
cell
2. Two zinc rods are placed in 0.1M & 1M ZnSO4 solution separately to form a cell. Give the
electrochemical representation of the cell & calculate its emf.

Solution: Cell representation

Zn(S)/ZnSO4 (0.1M) ZnSO4 (1M)/Zn(S)


0.0591 C2
E log
cell n C1
0.0591 1
E log
cell 2 0.1
0.0591
E log 10
cell 2

E 0.0295V
cell
3. Calculate the emf of the given concentration cell at 298K. Ag(s) /AgNO 3 (0.018M) AgNO3 (1.2M)
/Ag.
0.0591 C2
Solution : E log
cell n C1

0.0591 1.2
E log
cell 1 0.018
0.0591
E log 66.66
cell 1

E 0.1708V
cell

4. EMF of the cell Ag/AgNO3 (C1)// AgNO3 (C2=0.2M)/Ag is 0.8V. Calculate C1 of the cell.

Ecell = 0.0591/n logC2/ C1

0.8 = 0.591/1 log (0.2 / C1)

C1 = 5.5 X 10-14M

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5. The spontaneous galvanic cell Tin/Tin ion (0.024M)//Tin-ion (0.064M)/Tin develops an Emf of
0.0126V at 25OC. Calculate the valency of Tin.

Ecell = 0.0591/n logC2/ C1


0.0126 = 0.0591/n log (0.064/0.024)
n = 1.998 = 2.
Questions:

1. What is single electrode potential? Derive the Nernst equation for single electrode potential.
2. What are concentration cells? Deduce the expression for the EMF of a copper concentration cell.
3. Explain the construction & working of CALOMEL electrode.
4. Explain the measurement of electrode potential by using standard calomel electrode
5. Explain the construction & working of Ag/AgCl electrode
6. What is an ion selective electrode?
7. Explain the construction & working of GLASS electrode
8. Explain how glass electrode can be used in the determination of a PH of a solution.

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