Chapter 2

Electrochemical Energy System

8 March 2023 1
 Electrochemical Energy System
2.1 Electrochemical Cell
• ( A device, consisting of two electrode each in contact with
solution of its own ions, transforms the free energy change of
the redox reaction at the electrodes into electrical energy.)
• Energy is the driving force for chemical reaction in
electrodes.
• Chemical reaction involving transfer of electrons are called
oxidation and reduction reaction or redox reactions.
• Free energy change released in a reaction due to the
movement of charged particles give rise to a potential
difference.
• Maximum potential difference between the two electrodes
Electromotive force, (emf) or E, Unit- Volt (V).
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 Gibb’s free energy, ∆G is the negative value of the
maximum available electrical work.
 Electrical work, Wmax is the product of charge (q)
and the potential of the cell (E ). ( W = qE)

Work (J)
emf (V) = Charge (C)

E= -w/ q
w= -qE (q=nF)
w= -nFE
∆G = -nFE (Wmax = ∆G )
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 Standard condition; ∆Go= -nFEo
n = number of moles of electron
F = Faraday constant ( F =96485 C/mol)

 Working principle of a electrochemical cell is the

transformation of the change of free energy of the
redox reactions of the electrodes into electrical energy.

∆G = -nFE ( E = + ve)

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 Electrochemical cells

Voltaic cell Electrolytic Concentration

(Galvanic cell) Fuel cell
cell cell

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Voltaic cell or Galvanic cell
• Energy is released from spontaneous redox reaction

• System does work on load /surroundings

• Anode (- ve) : oxidation

• Cathode (+ ve) : reduction

• Free energy change of electrode redox

• reactions are converted into electric
• energy.
•

∆G = -nFE

Primary irreversible cells ( dry cells)

 Secondary cells (lead storage battery) and Ni – Cd battery

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 Electrolytic cell
• Energy is absorbed to drive non-spontaneous redox reaction

• Surroundings (power supply) do work on system (cell)

• Anode (+ ve) : oxidation

• Cathode (- ve) : reduction

-nFE = ∆G

• non-spontaneous direction by external force and the free energy change (∆G) is
• positive.

• Eg. Molten sodiun chloride

• Aqueous sodium chloride

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 Concentration cell

• Electrochemical device that generates electrical energy

• Two electrode of the same metals

• Solutions of its ions at different concentrations

• Free energy change of electrode reactions are converted into

• electrical energy.

∆G = -nFE

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 Fuel cell

• Electrochemical device which operates with continuous replenishment of the fuel

• No charging is required

• Free energy change of electrode redox reactions are converted into electric
energy.

∆G = -nFE

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2.2 Difference between a Galvanic cell and
Electrolytic Cell

Galvanic cell Electrolytic Cell

1. Chemical energy into electrical 1. Electrical energy into chemical energy

energy
2. Spontaneous 2. Non-spontaneous and takes place only
when electrical energy is supplied
3. Dissimilar metal 3. Dissimilar metal or same metal

4. Each metal is dipped in its own ion 4. Only one electrolyte is taken

5. Separate compartments 5. Both electrode are inserted in the same

electrolyte solution
6. Two electrolyte solutions are 6. No salt bridge is needed
connected by a salt bridge
7. – ve electrode is anode 7. + ve electrode is anode
+ ve electrode is cathode - ve electrode is cathode

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 2.3 A Daniel cell

• Best of galvanic cell

• Two electrode of dissimilar metals (Zn,Cu)
• Solution of own ions ( ZnSo4, CuSo4)
• Two solution are connected by a salt bridge
• Two half cell

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If EoCu2+ /Cu > EoZn2+ /Zn, Spontaneously and cell potential is + ve.
 Tendency of Zn (lower reduction potential) to dissolved and
form Zn2+ ions is greater than the tendency of Zn2+ ions to get
deposited, Zn half cell acquire negative charge.

 Tendency of Cu (higher reduction potential) to go into

solution as Cu2+ ions is less than the tendency of Cu2+ ions to
get deposited, Cu half cell become positive charge.

 Zn is negative electrode (anode), Cu is positive electrode

(cathode). Electrons flow from the zinc half cell to the copper
half cell in the Daniel cell.

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-galvanic cell ------- two electrodes of dissimilar metals, Zn & Cu
[each electrode is in contact with a solution of its ions ;
ZnSO4 and CuSO4 ]
------- two solutions are connected by a salt bridge

At the anode , Zn → Zn 2+ + 2e (oxidation)

At the cathode, Cu 2+ + 2e → Cu (reduction)
overall redox reaction Zn + Cu 2+ → Zn 2+ + Cu

If EO Cu 2+/ Cu ˃ EO Zn2+/ Zn ------------- spontaneously, potential (+)ve

In Daniel cell,
The tendency of Zn to dissolve and form Zn 2+ ion > the tendency of Zn 2+ to be
deposited as Zn
∴ Zn half – cell acquires negative charge (lower reduction potential)

The tendency of Cu to dissolve and form Cu 2+ ion < the tendency of Cu 2+ to be

deposited as Cu
∴ Cu half – cell acquires positive charge (higher reduction potential)

IUPAC : Zn -------- negative electrode -------oxidation (anode)

Cu -------- positive electrode ---------reduction (cathode)
 2.4 Electrochemical conventions

1. Sign of electrode potential (At reduction potential)

At cathode Mn+ + ne- M EoMn+ /M = +ve

At anode Mn+ + ne- M EoMn+ /M = -ve

2. Representation of electrode
M / Mn+( C1) (oxidation) eg. Zn/Zn2+
Mn+(C2) / M (reduction) eg. Cu2+/Cu

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3. Representation of a cell
(a) Anode is always on the left hand side
M / Mn+(C1) (oxidation) eg. Zn/Zn2+

(b)Cathode is always on the right hand side on the anode

Mn+(C2) / M (reduction) eg. Cu2+/Cu

(c ) Two vertical line (||), Between the two salt solution

M / Mn+(C1) ||Mn+(C2) / M

eg. Zn/Zn2+ (C1 )|| Cu2+/Cu (C2)

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4. Emf of a cell
Eocathode > Eoanode

EMF of a cell is defined as algebraic difference between the

reduction potentials of the cathode and anode.

Ecell = Eocathode - Eoanode

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5. Electrode and Cell reactions
(a) At anode
M1 Mn+1(C1) + ne (oxidation)

(b)A cathode
ne +Mn+2 (C2) M2 (reduction)

Net reaction, M1 + Mn+2 Mn+1 + M2

∆G = -nFE

Emf of the cell is +ve, Eocathode > Eoanode

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Example 2.1 The electrodes reduction potentials of Zn
and Cu electrodes are -0.76 and +0.34 V
respectively.
Calculate the EMF of the Daniel cell.

EO Cu2+/Cu ˃ EOZn2+/Zn
At anode, Zn → Zn 2+ + 2e (oxidation) EO ZnIZn2+ = + 0. 76 V
At cathode , Cu2+ + 2e → Cu (reduction) EO Cu2+/Cu = 0.34 V

E0cell = EO Cu2+/Cu - EOZn2+/Zn

= 0.34 - (-0.76)
= 1.10 V
Eg 2.2. Represent a cadmium copper cell. Give the electrode
and net cell reactions. If the standard reduction potentials af Cd
and Cu are -0.40 and 0.34V respectively. Calculate the standard
emf of the cell.
Solution; Eocathode > Eoanode
EoCu2+ /Cu > EoCd2+ /Cd
(i) Cell representation Cd/Cd2+ || Cu2+/Cu
(ii) At anode
Cd Cd2+ + 2e (oxidation ) EoCd / Cd2+ = 0.4 V
At cathode Cu2+ + 2e Cu (reduction) EoCu2+ /Cu = 0.34 V

(iii)Net reaction, Cd + Cu2+ Cd2+ + Cu

( iv)Emf of the cell, Eo cell =Eocathode – Eoanode

= EoCu2+ /Cu– EoCd2+ /Cd = 0.34 –(-0.4) = 0.74 V

19
* Reduction reaction
Example 2.3 The oxidation potential of a nickel half cell is 0.25 V and the
reduction potential of a silver half cell is 0.80 V .(a) Represent
nickel- silver cell (b) Give their electrode and net cell reactions
and calculate the standard emf of the cell.

EO Ag+/Ag ˃ EONi2+/ Ni
Ni acts as the anode and Ag acts as the cathode.

2+ +
(a) cell representation Ni / Ni II Ag / Ag

(b) electrode reactions

At anode, Ni → Ni2+ + 2e (oxidation) EO Ni INi2+ = + 0. 25 V
At cathode , Ag+ + e → Ag (reduction) EO Ag+/Ag = 0.80 V

the net cell reaction Ni + 2 Ag+ → Ni2+ + 2 Ag

(iii) E0cell = EO cathode - EOanode

= EO Ag+/Ag - EONi2+/Ni
= 0.80 - (-0.25)
= 1.05 V
2.5 The Origin of Electrode Potential
Metal piece is dipped in water or a solutions of its own
ion, the observed is zero because rate of oxidation process of
the metal a situation is equal to the rate of reduction at the metal
surface.
Electrode potential is zero.

Formation of the Helmholtz electrical double layer at

the metal and ionic solution
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 -dissimilar metal electrodes (half cells reaction ; M1 and M2 )

• - the redox reactions take place at the two half cells a dynamic
equilibrium between the +ve/-ve charges at the electrode
interface.
• opposite charges at the respective electrodes
• +ve (a ) or –ve (b) ion remains close to the metal.
• This charged layer around an electrode is called the Helmholtz
electrical double layer.

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2.6 Electrode Potential
1. Single Electrode potential
– Two electrode of metal (two dissimilar metal)
- Difference in their standard electrode potential
S.E.P can be defined as the potential established at the interface between the metal
(M) and the ion solution (Mn+) , in contact with a solution of its own ions.
(E0 Mn+/ M or E0 M/Mn-)

Value of S.E.P ( E) ,in a cell depend on (a) the nature of metal electrode, M. (b) the
concentration of metal ions , Mn+ (c ) the temperature.

2. Standard Electrode potential ( Electrochemical series)

- Standard Electrode potential of a large number of half self by SHE
(Standard Hydrogen Electrode) as the reference electrode (Eo =0), St.E.P is defined
as the potential of an electrode measured at 298K and 1M metal in concentration.
SEP of two half –cells are denoted Eo Mn+ / M (or) M/ Mn+

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3. Application of Electrochemical series
i). Comparison of the relative oxidizing and reducing power
F2 = 2.87 , Li+ =(- 3.04)
• F2 can be reduced most easily, Li+ are reduced with greet
difficulty.
• Other world Li+ ion will be oxidized most easily and best reducing
agent
ii).Relative activities of the metal
Mg> Zn> Cu> Ag
iii).To calculate the standard of emf
-oxidation and reduction reaction occur at the electrode
iv). To predict the spontaneity of redox reaction
-Free energy change in a galvanic cell, or spontaneous
reaction (negative). Emf = +
Other world, emf of the cell is negative, redox reaction
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2.7 Measurement of Electrode Potential and IUPAC
The single Electrode potential of half self can be determined always
by reference electrode, (SHE)
1. Determination of Standard Electrode potential of the cathode

Mn+ + 2e M
Pt /H2(g) (1atm) / H+(1M) //Cu2+(1M) / Cu
At anode, H2 2H+ + 2e
At cathode, Cu2+ + 2e Cu
E0Cu2+/ Cu > E0SHE
According to the electrochemical convention. “ the potential of a
copper electrode is taken as + ve”
E0cell = E0Cu2+/ Cu - (0)= E0Cu2+/ Cu
E0Cu2+/ Cu is positive,
E0cell = E0Cu2+/ Cu - E0H2 = 0.34 – 0 = 0.34 V
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2. Determination of Standard Electrode potential of the anode
Zn /Zn2+ (C1)// H+(C=1M) /H2 (1atm) /pt
E0SHE > E0Zn2+/ Zn

At anode, Zn Zn2 + 2e E0Zn/Zn2+ =0.76 V

At cathode, H+ + 2e H2 E0H+/ H2 = 0

EMF of the cell, E0cell = E0cathode - E0anode = E0H+/ H2 - E0Zn2+/ Zn

E0 = 0 - E0Zn2+/ Zn = - (- 0.76) = 0.76V
E0Zn/Zn2+ = 0.76 V (oxidation potential)
= - 0.76 V ( Reduction potential)
`
E0oxidation = - E0reduction
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2.8 Derivation of Nernst Equation for the Single Electrode
Potential

At cathode , Mn+ + ne M

∆G = ∆ Go + RT Ln K
(- Wmax = ∆G )
∆G = ∆ Go + 2.303 RT Log K
[𝑀]
K = [M 𝑛 +
[𝑀]
∆G = ∆ Go + 2.303 RT Log [M 𝑛+
∆G = -nFE
1
-nFE = nFEo + 2.303 RT Log [ 𝑀𝑛+
]

Dividing by -nF
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Dividing by -nF

2.303.𝑅𝑇 1
E= Eo - Log [ ]
𝑛𝐹 𝑀𝑛+

2.303.𝑅𝑇
At cathode, E= Eo + Log Mn+
𝑛𝐹

2.303.𝑅𝑇
At anode, E= Eo - Log Mn+
𝑛𝐹

For EMF of the Cell, M1 / Mn+(C1) ||Mn+(C2) / M2

M1 + Mn+2 Mn+1 +M2

+ [𝑃𝑟𝑜𝑑𝑢𝑐𝑡]
2.303.𝑅𝑇 𝑀1𝑛
Ecell = Eo - Log [ 𝑀2𝑛
+ ] [ Reactant]
𝑛𝐹
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Example 2.4 (Pg.55)
Write an express for the emf of a Daniel cell.
If E0 cathode ˃ E0 anode , the net cell reaction
Zn + Cu2+ ⇌ Zn2+ + Cu

Ecell = E0 cell - 0.0591 log10 Zn2+

2 Cu2+

E0cell = EO cathode - EOanode

= EO Cu2+/Cu - EOZn2+/Zn
= 0.34 - (-0.76)
= 1.10 V

Ecell = 1.1 - 0.0591 log10 Zn2+

2 Cu2+
Eg 2.5. Determination of standard electrode potential, Eo of copper is
0.34V and the concentration of Cu2+ ion is 0.015M. Find the (i)
reduction electrode potential, E of the copper and (ii) free energy
change of electrode potential.
Solution, Cu2+ + 2e Cu
(i) Nernst equation for single reduction electrode potential, E is

2.303.𝑅𝑇
E= Eo + Log [Cu2+ ]
𝑛𝐹
0.0591
E= Eo + Log [Cu2+ ]
𝑛

0.0591
Ecell = 0.34 + Log [0.015 ]
𝑛

Ecell = 0.296 V
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(ii) n = 2 mol , E = 0.296 V, F = 96500 C/mol

∆G = -nFE

∆G = - [2 x 96500 x0.296]
= - 57128 volt-coulomb
= - 57.13 KJ/mol (volt-coulomb = Joule)

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Example 2.6 The standard reduction electrode potential of
copper and zinc are 0.34 V and – 0.76 V
respectively. If the develop an EMF of 1.10 V , find the free energy
change of the overall cell reaction.
Zn + Cu2+ → Zn2+ + Cu

Δ G0 = - nFE0
Δ G0 = - [ 2 x 96500 x 1.1] = - 212,300 J = - 212.3 kJ/mol
Δ G0 = - 212.3 kJ/mol

The cell reaction is spontaneous because of the decrease of free

energy - 212.3 kJ/mol.
Eg 2.7. The EMF of cell, Cd(s) / Cd2+ (0.01M) // Cu2+ (0.5M)/ Cu is
0.79 V. Determination of standard electrode potential of Cd
electrode, If the standard electrode potential of copper is 0.34V.

Solution; Nernst equation for EMF cell,

Cd(s) / Cd2+ (0.01M) // Cu2+ (0.5M)/ Cu Ecell = 0.79 V
EoCu2+ /Cu = 0.34 V, EoCd / Cd2+ = ? V
Cd + Cu2+ Cd2+ + Cu

2.303.𝑅𝑇 Cd2+
Ecell = Eocell - Log [ Cu2+ ]
𝑛𝐹
0.0951 Cd2+
Ecell = Eocell - Log [ Cu2+ ]
𝑛
0.0951 0.01
0.79 = Eocell - Log [ ]
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2 0.5 33
 0.0951 0.01
0.79 = Eocell - Log [ ]
2 0.5

0.0951 0.01
Eocell = 0.79 + Log [ ]
2 0.5

Eocell = 0.79 +0.05 = 0.74 V

Eocell =Eocathode – Eoanode = EoCu2+ /Cu– EoCd2+ /Cd

0.74 = 0.34 – EoCd2+/Cd

EoCd2+ /Cd =0.34 – 0.74 = - 0.40 V

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Example 2.11 Consider the following cell :
Fe/ Fe2+ (0.02 M) II Cd2+ (1 M) /Cd. (i) write the cell reaction
and (ii) calculate the EMF of the cell and determine the direction of the
spontaneous reaction . Given the standard reduction potentials of Fe and Cd
are – 0.44 and -0.40 V respectively.
EO Cd2+/Cd ˃ EOFe2+/ Fe

Fe/ Fe2+ (0.02 M) II Cd2+ (1 M) /Cd

At anode, Fe → Fe2+ + 2e EO Fe2+/Fe = - 0.44V
At cathode , Cd2+ + 2e → Cd EO Cd2+/Cd = - 0.40 V
the net cell reaction Fe + Cd2+ → Fe2+ + Cd

E0cell = EO cathode - EOanode

= EO Cd2+/Cd - EOFe2+/ Fe
= -0.40 - (-0.44) = 0.04 V

E = E0 - 0.0591 log10 Fe2+

2 Cd2+

E = 0.04 - 0.0591 log10 0.02

2 1
= 0.04 + 0.0503 = 0.09V [emf= (+) ∴ spontaneous ]
Example 2.13 Calculate the voltage of the cell, Mg/ Mg2+ II Cd2+ /Cd.
at 25 °C when [Cd2+ ] =7 x10-11 M and [Mg2+ ] =1 M and
E0cell = 1.97 V.

At anode, Mg → Mg2+ + 2e
At cathode , Cd2+ + 2e → Cd
the net cell reaction Mg + Cd2+ → Mg2+ + Cd

Ecell = E0 cell - 0.0591 log10 Mg2+

2 Cd2+

Ecell = 1.97 - 0.0591 log10 1

2 7 x 10-11
= 1.67 V
Example 2.14 Calculatethe voltage generated in following cell :
Mn I Mn2+ II Fe2+ / Fe , when the iron rod is
immersed in 1.0 M FeSO4 solution and the Mn rod is immersed in 0.1 M
MnSO4 solution. Given EOFe2+/ Fe = -0.4 V and EO Mn2+/Mn = -1.18 V.

EOFe2+/ Fe > EO Mn2+/Mn

Mn I Mn2+(0.1M) II Fe2+ ( 1M )I Fe
At anode, Mn → Mn 2+ + 2e EO Mn I Mn2+ = 1.18 V
At cathode ,Fe2+ + 2e → Fe EOFe2+/ Fe = -0.4V
the net cell reaction Fe2+ + Mn → Fe + Mn2+

E0cell = EO cathode - EOanode

= EO Fe2+/ Fe - EOMn2+/ Mn
= -0.4 - (-1.18 ) = - 0.78 V

Ecell = E0cell - 0.0591 log10 Mn2+

2 Fe2+
Ecell = - 0.78 - 0.0591 log10 0.1 = 0.78 + 0.02955 = 0.8096 V
2 1
Eg 2. 17 Write the electrode reaction and calculate the EMF of the
following cell at 298 K. Given Eo = 0.46 V
Cu(s) / Cu2+ (1x 10-2M) // Ag+ (1x 10-1M)/ Ag (s)
Solution,
At anode, Cu Cu2+ + 2e
At cathode, 2Ag+ + 2e 2Ag

Over all, Cu + 2Ag+ Cu2+ + 2 Ag

Eocell =Eocathode – Eoanode = 0.46 V

2.303.𝑅𝑇 Cu2+
Ecell = Eocell - Log [ (Ag +)2 ]
𝑛𝐹
0.0951 1x 10−2
Ecell = 0.46 - Log [ (1x 10−1 )2 ] = 0.46V
2
8 March 2023 38
 2.10. Types of Electrodes or Half cells
1. Metal –Metal Ion Electrode- M Mn+ +ne (redox reaction)
2. Metal –Metal Salt- Ion Electrodes
– Calomel electrode, Hg/ Hg2Cl2/Cl-
- Sliver- silver chloride electrode, Ag/ AgCl/Cl-
3. Gas Electrodes
Pt/H2(g) (1atm) / H+ (C=1M) (at cathode)
4. Oxidation-Reduction Electrodes
The same metal at an inert electrode like Pt,
Pt/ Fe2+ :Fe3+ : Pt/ Sn2+ : Sn4+
5. Ion Selective Electrodes (ISE)
eg; Glass ISE, Calcium ISE, Ammonium ISE..etc
- Membrane of half- cell sensitive electrode
- Voltage developed between the sensing and the reference
electrode
8 March 2023 39
 5. Ion Selective Electrodes (ISE)
A Membrane of a half cell is sensitive to a particular ion in
a solution, ion exchange process takes place between the
membrane electrode and the solution containing the specific ions
and develops a potential, which depends on the concentration of
that particular ionic species. eg; Glass ISE, Calcium ISE..etc
ISE (or chemical sensors) are miniature analytical devices
that are used to interface between chemical species and
electronic devices., which can provide information on the
presence of specific ions (or compounds) in samples. The
potential developed at the ion sensitive sensor is a measure of
the concentration of the ionic species of interest.
Ion selective membrane is the key component of all
potentiometric ion sensors. The voltage developed between the
sensing and the references electrode is a measure of the
concentration of the reactive ion measured. The voltage
measured between two electrode.
40
 2.11. Types of Ion Selective Electrodes
1. Glass Membrane Electrodes- are Formed by the doping of the
silicon dioxide glass matrix with various chemicals. The most common
glass membrane electrode is the pH electrode. GME are also available
for the measurement of sodium ions. GME exchange H+ ions from an
acid solution. Gl- Na+ + H+ ↔ Gl- H+ + Na+
2. Polymer Membrane Electrodes- consist of various ion exchange
materials in an inert matrix such as PVC, silicone rubber. Eg. Potassium,
Calcium and Nitrate –ISE.
3. Solid State Electrodes- utilize relatively insoluble inorganic salts in a
membrane. SSE exist in homogeneous or heterogeneous form. Eg;
silver, chloride and fluoride.
4. Gas Sensing Electrodes- are available for the measurement of
ammonia, carbon dioxide, nitrogen oxide and sulfur dioxide. These
electrode have a gas permeable membrane and an internal buffer
solution. The pH of the of the buffer solution changes as the react with
it. 8The change is detected by a combination pH sensors within41 the
March 2023
2.12. Application of Ion Selective Electrodes (ISE)

• Water Hardness ( Calcium ISE)- Calcium is very useful as an

indicator of hardness of water in fresh water samples.
• Nitrate Monitoring (Nitrate ISE)- ISE can be used to qualitatively
determine the concentration of the nitrate ion in fresh water
samples.
• Salinity and Chloride Monitoring in Sea Water (Chloride)- ISE can
be used to determine the concentration of chloride ion or salinity
levels in sea water samples.
• Monitoring Steam for Ammonium (Ammonium ISE)- Ammonium
is often present as a result of water runoff from fertilised field. ISE
gives you an easy wat to check for this environmental important
ion.
• Calcium in milk (Calcium ISE)- ISE can be used to determine
calcium levels in skim milk.
8 March 2023 42
 2.13. How an Ion Selective Electrodes Works

Ion selective electrodes are membrane based electrodes that

measure a specific ion (eg, Na+, Ca2+ ) in aqueous solution .
When the membrane of the electrode is in contact with a
solution containing the specific ion, a voltage, dependent on the level
of that ion in solution develops at the membrane.
All ISE’s measure the specific ion concentration directly.
Samples need to be aqueous to avoid contaminating or dissolving the
membrane.
The voltage developed between the sensing and the reference
electrode is a measure of the concentration of the reactive ion being
measured.
As the concentration of the reacting ion at the sensing
electrode various, so does the voltage measured between two
electrode.
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2.14. Reference Electrodes

The purpose of the reference electrode is to complete the measuring

circuit and provide a stable and reproducible potential against which the
indicator electrode is compared and measured.
The reference electrode is designed to produce the same potential no
matter in what solution it is placed.
(There are few half-cells whose electrode potentials are known, that
provides a stable, reliable and reproducible potential against which the
indicator electrode is compared , so that they can be used repeatedly with
accuracy. These electrodes of reproducible and the stable potentials are
called the reference electrode.)
Thus, the potential of any other electrode can be measured when it is
coupled with any of these reference electrode.

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1. Primary Standard Hydrogen Electrode (SHE)

A common reference electrode used to measure the potential of the

another electrode is the Standard Hydrogen Electrode (SHE) whose
electrode potential at all temperatures is taken as zero, ie; E0 =0

SHE; Pt/H2(g) (1atm) / H+ (1M)

2H+ + 2e H2(g)

E = Eo + 0.0591Log [H+ ]

If [H+ ] = 1 M and H2 is bubble at 1atm at 298 K

E = Eo = 0
Fig 2.7 Standard Hydrogen Electrode

8 March 2023 45
2. Secondary Reference Electrodes
(i) calomel Electrodes- The most widely used reference
electrode in a electrochemical cell is the calomel electrode.
The potential of an calomel electrode is found to depend
on the concentration of KCL solution used in the half cell.

Concentration of KCl Calomel (Eo )

0.1 N 0.3334 V
1.0 N 0.2810 V
Saturated 0.2422 V

Generally, a calomel Electrode with saturated KCl

solution is used in electrochemical cells.

8 March 2023 Fig 2.8 Dipping type of calomel Electrode

46
Construction :
A calomel electrode consist of a narrow glass tube,
The bottom of which has a layer of Hg and followed by a paste
of Hg2Cl2 and Hg. The remaining portion of the glass tube is
filled with saturated KCl solution.

A pt ware is dipped into the Hg layer for electrical contact. This

is placed inside an outer glass jacket with a tapering porous
end and is filled with saturated KCl solution. The calomel
electrode is represented as
Hg/ Hg2Cl2/Cl-
Calomel reaction, Hg2Cl2 + 2e 2Hg + 2Cl-

Reduction electrode potential, E = Eo - 0.0591Log [Cl-]

8 March 2023 47
Demerits of a Calomel Electrodes
Calomel electrodes should not be used above 50 ℃
because the mercury chloride breaks down, yielding unstable
readings.
It has similar stability to silver/silver chloride and a better
thermal hysteresis. It is less prone to contamination because
the mercury chloride interface is protected inside a tube and is
not in direct contact with the electrolyte.

Reproducibility of a calomel electrode is much better

than a silver/ silver chloride. Recently calomel has fallen into
disfavour because of its toxicity.

8 March 2023 48
(ii) Silver- Silver Chloride Electrode -The electrode is an
example of a metal- metal salt ion reference electrode. It
consist of a silver electrode coated with a sparingly soluble
AgCl and is immersed in a solution containing Cl- ions
(saturated KCl)
Commercial reference electrodes consist of a plastic
tube electrode body. The electrode is a silver wire that is
coated with a thin layer of silver chloride, either by
electroplating or dipping the wire in molten silver chloride.

Ag/ AgCl/Cl-

AgCl + e Ag + Cl-

E = Eo - 0.0591Log [Cl-]

8 March 2023 49
Fig. 2.9 A Silver- Silver Chloride Electrode
 Merits of Silver- Silver Chloride Electrode

• The reduction electrode potential of thesis electrode is

dependent on the concentration of Cl- ions.

• Its ease of manufacture and its superior temperature range

males it usable even above 130 ˚C.

• The potential of the electrode remain constant as long as the

chloride concentration remains constant.

• It is used today by many electrochemists because it is

sample, inexpensive, very stable and non- toxic.

8 March 2023 50
 Application of Silver Chloride

• Reference electrodes. eg; in pH meter

• Photography films and plate

• Infrared windows where it can be in contact with many

aqueous solutions, eg FT IR spectrometers, in which case it
can be an alternative to KBr, which is attacked by water.

8 March 2023 51
 2.15 What Factors Can Effect A Reference Electrode

• The potential of a reference electrode varies with temperature.

• The potential of the silver/ silver chloride and calomel

reference electrode are also affected by the concentration of
chloride in the electrode solution, which must be maintained at
a constant value by proper storage

8 March 2023 52
2.16 Limitations Of Primary Reference Electrode And
Advantages Of Secondary Reference Electrode
• (i) difficult to maintain H+ ion concentration as 1M.
• (ii) difficult to maintain a flow of 1 atm of hydrogen at the
interface of Pt electrode.
• (iii) impurities present in hydrogen flow may poison the Pt electrode
which alters the potential value.

• Advantages over primary reference electrode

• (i) they have constant and stable potential values at a particular
temperature.
• (ii) they are calibrated with respect to SHE.
• (iii) they have the least potential gradient with temperature.
• (iv) the potential values are reliable and measurements can be
made with great accuracy.

8 March 2023 53
2.17 Ion – Selective Electrode

1. Glass Electrode – A glass membrane of silicate glass is found to

be sensitive to hydrogen[H+] ions of an acidic solution. The
membrane undergoes ion exchange reaction, the Na+ ions of glass
are exchanged for H+ ions.
[H+] + Na+Gl- Na+ + H+ Gl-
(membrane) (membrane)

When a thin walled glass bulb containing N/10 acid HCl solution, as
shown in fig, is immersed in an acid solution of different
concentration [C1> C2], a “ boundary potential, Eb ” is developed
across the gel layers of the glass membrane. i.e, Eb = E1 - E2

2.303𝑅𝑇 C1
Eb =E1 - E2 = Log [ C ]
𝑛𝐹 2
8 March 2023 54
 2.303𝑅𝑇
Eb =E1 - E2 = Log [ CC1 ]
𝑛𝐹 2

0.0591
Eb = Constant + Log10 [C1]
𝑛

0.0591
=Constant + Log10 [H+],
𝑛

pH = -Log10 [H+]
Eb = K – 0.0591 pH

C1 is the concentration of H+ ions of the solution into which the

glass membrane is dipped . The concentration of H+ ions C2
inside the bulb is constant

8 March 2023 55
Construction of Glass Electrode – A glass membrane electrode is made
up of a thin long glass tube with a thin walled glass membrane at the
bottom end. A low melting point and high electrical conductance silicate
glass.
Ag/ AgCl/ N/10 HCl solution / Glass
EG =Eb + EAg/AgCl
Theoretically, Eb = 0, when C1= C2 , Easy= a small addition, potential
contribution exists, even C1= C2
EG =Eb + EAg/AgCl + Easy

EG = [ K – 0.0591 pH] + EAg/AgCl + Easy

EG =E0G – 0.0591 pH
EG =[ K + EAg/AgCl + Easy ] , is constant for a particular glass material.
The above expression indicates that the potential of a glss electrode, EG
varies with the pH of the acidic solution.
8 March 2023 56
2.18 Determination of PH of a Solution Using Glass and a
Calomel Reference Electrode
( glass electrode is couple with SCE to determine the pH of an acidic
solution)

Hg/ Hg2Cl2/Cl- // (unknown) H+ solution / Glass electrode

EG > ESCE (glass electrode is higher than reference SCE)

Ecell = Ecathode – Eanode = EG - ESCE (EG =E0G – 0.0591 pH )

= [E0G – 0.0591 pH] -- ESCE

E0G = K + EAg/AgCl + Easy

0.0591 pH =E0G – ESCE - Ecell

E0G – ESCE − Ecell

pH = =
0.0591
8 March 2023 57
 2.19 Determination of PH of a Solution Using Glass and a
Common Silver- Silver Chloride Reference Electrode

Combined Glass Electrode The heart of the

glass electrode is a thin glass membrane, specially
fabricated to preferentially exchange H+. The
outside of the membrane is in contact with the
analyte solution containing the unknown [H+]. The
inside of the membrane contacts a hydrochloric
acid solution of fixed (N/10) concentration. A silver
wire, coated with AgCl dips into this solution, the
other end of the wire is connected to the
measuring device. A combination glass electrode
with Ag/AgCl reference may be represented as
shown in fig.
8 March 2023 58
Construction and the Mechanism of the Response of pH Electrode
• H+ ion concentration change in the composition of the glass membrane
due to an ion exchange process involving the solution and membrane.
Membrane potential, proportional to pH, is measured. All other potentials
are constant. The membrane potential is measured against two fixed
potentials, the external reference and the internal reference both Ag/AgCl
reference electrode.
• An Ag/ AgCl/CL- electrode is immersed inside the bulb containing N/10
HCl (C1) solution. The outer interface of the glass bulb is in contact with
the H+ ions of unknown (C2) solution a shown in fig. The Ag/AgCl/Cl-
electrode in the combined glass cell behaves as a commom reference
electrode for both the inner and outer H+ ions.
• If C2 > C1,

[combined glass electrode]

Ag/ AgCl/CL(aq)- // H+ (aq. Inside)|| H+ (aq.outside)/Cl-/AgCl(s) /Ag(s)

8 March 2023 59
Ecell = E0 cathode – E0 anode

= ISE – Ag / AgCl
• = Eb + Easy – E0 Ag / Ag Cl (Eb = K- 0.0591 pH )

• = K – 0.0591 pH + Easy – E0 Ag /AgCl ( E0G =K+ Easy )

• Easy = the potential contribution exist even C1 = C2

• The potential of the cell is given
•
• E cell = [ E0 G – 0.0591 pH ] –E0 Ag /AgCl

• = E0 G – 0.0591 pH – E0 Ag /AgCl
• 0.0591 pH = E0G – Ecell – E0 Ag/ AgCl
𝑬𝟎𝑮 −𝑬𝒄𝒆𝒍𝒍 −𝑬𝟎 𝑨𝒈 𝑨𝒈𝑪𝒍
• pH = /
𝟎.𝟎𝟓𝟗𝟏

8 March 2023 60
 2.20. Concentration Cell
The electrode potential of a half cell varies with the
concentration of the metal ions around the interface of the electrode
in solution. Unlike a galvanic cell, in a concentration cell two similar
metal electrodes are in contact with the solutions of its ions at
different concentrations, resulting in difference in their electrode
potentials.
A concentration cell is also an electrochemical device that
generate electrical energy when two electrodes of the same metal are
in contact with solution of its at different concentrations.
Cu / Cu2+ (C1) // Cu2+ (C2) / Cu
C1 and C2 are molar concentration of the Cu2+ ions in contact with two
copper electrodes; If C2> C1

8 March 2023 61
At anode Cu 2e + Cu2+ E0 Cu / Cu2+ = - ve V (Oxidation)

At cathode Cu2++ 2e Cu E0 Cu2+ /Cu = + ve V (Reduction)

Net Reaction, Cu2+ (C2) Cu2+ (C1)

Voltage of cell exist as long as C2 > C1

Eo cell =Eocathode – Eoanode

0.0951 0.0951
Ecell = [Eocell + Log C2] – [Eocell + Log C1]
𝑛 𝑛

Ecell = [E0 Cu2+ /Cu - E0Cu /Cu2+ ] = 0, E0 Cell = 0 (both

electrodes are the same material, copper)
𝟎.𝟎𝟗𝟓𝟏 𝑪𝟐
Eocell = Log [ C ]
𝟐 1
8 March 2023 62
Eg 2.21. A concentration cell is constructed by dipping two copper
electrode in 0.001 M and 0.1 M CuSo4 and the two solutions are
connected by a salt bridge. Calculate the EMF of cell at 297K. Since
0.1M> 0.001M, the electrode that is in contact with higher Cu2+ ion
concentration acts as cathode .
Solution ;
Cu(s) / Cu2+ (0.001M) // Cu2+ (0.1M)/ Cu
At anode Cu Cu2+ (0.001M) + 2e
At cathode Cu2+ (0.1M) + 2e Cu
Cu2+ (0.1M) Cu2+ (0.001M)

0.0951 C2
Ecell = Log [ C1 ]
𝑛
0.0951 0.1
Ecell = Log [ 0.001 ]
2
8 March 2023
=0.0591V 63
When a metal rod is dipped in a solution of its own ions, the potential developed depends on
A. Concentration of the solution
B. Temperature of the solution
C. Both (i) and (ii)
D. Pressure of the solution

In glass electrodes, a potential is produced across the membrane which is used to measure
A. Basicity of the solution
B. Single electrode potential
C. pH of the solution
D. None of these

Pt / Fe2+ , Fe3+ electrode is an example of

A. Metal-metal ion electrode
B. Metal- metal salt ion electrode
C. Oxidation- reduction electrode
D. Ion – selective electrode

Greater value of standard reduction potential, greater will be tendency

A. To get oxidized
B. To accept electrons
C. To get reduced
D. Both (ii) and (iii)
8 March 2023 64