COURSE TITLE: APPLIED CHEMISTRY COURSE CODE:

Electrochemistry: Electrode Systems and Corrosion 08 hours

Electrodes and Cells – Introduction- Classification of cells - primary, secondary and
concentration cells; Reference electrodes - Calomel electrode; Ion-selective electrodes - Glass
electrode. Determination of pH using glass electrode, numerical on concentration cells.

Corrosion - Definition, Electrochemical theory of corrosion, Types of corrosion - differential

metal, differential aeration and stress corrosion; Factors affecting the rate of corrosion; Corrosion
Penetration Rate (CPR), numerical. Corrosion control: Cathodic protection – Sacrificial anode,
Impressed current method. Metal finishing - Introduction, technological importance; Electroless
plating: Introduction, Electroless plating of copper (PCB). Inorganic coatings – anodizing and
phosphating.

Self-study: Galvanic series and its importance, Electroplating of Chromium

NOTE:

HIGHLIGHTED PART-BASIC UNDERSTANDING ONLY-NOT IN SYLLABUS

ELECTROCHEMISTRY

Introduction
“It is a branch of chemistry that deals with the inter conversion of chemical and electrical
energies.”

− The application of electrochemistry is found in many areas including chemistry,

physics, engineering, biology, electronics, computers, metallurgy and material
science.
− Electroplating (Metal finishing), extraction of metals (like Na, Al, Mg, etc), refining
of metals (like Cu, Al, Au, etc), electronic and medical devices working on portable
energy, batteries work on the principle of electrochemistry.

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Electrochemical cells: The device which converts chemical energy to electrical energy or
vice versa.
Electrode: An electrode is an electrical conductor used to make contact with a non-
metallic part of circuit.
Anode: It is the electrode at which oxidation occurs.
Cathode: It is the electrode at which reduction occurs.
Redox reaction: A chemical reaction in which both oxidation and reduction reaction
occur simultaneously.

Additional Info:
Conductors

Metallic Conductors Electrolytic Conductors

− Allow electricity to pass through them - pass electricity through them in their
Without undergoing chemical change molten/aqueous solution
− Due to flow of electrons - due to charged particles (ions)

Electrode Potential (E):

The potential developed at the interface between the metal and the solution when it is in
contact with a solution is called electrode potential.
− When a metal is immersed in a solution of its own ions, two types of process take
place.
− Metal may undergo oxidation, goes in to solution as ions losing electrons.

− Metal ions in the solution may undergo reduction and get deposited as metal
atoms on the metal surface (electrode surface).

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 − When a metal undergoes oxidation, it loses positive ions in to solution leaving
behind a layer of negative charges on its surface. This layer attracts positive
charges and form electrical double layer, also called as Helmholtz electrical double
layer.

− The resultant potential difference between the electrode (metal) and the solution
is termed as electrode potential.

Standard electrode potential: The potential developed at the interface between the metal
and the solution when it is in contact with a solution of unit concentration at 298 K at 1
atm pressure is called standard electrode potential.

Galvanic Cell: (For understanding: Not in the syllabus)

 Galvanic cell is an electrochemical cell which converts chemical energy in to
electrical energy.
 It consists of two electrodes dipped in two electrolytic solutions.
 The two solutions are separated by a porous diaphragm called as salt bridge.
 Example for galvanic cell is Daniell cell. In the Daniel cell, zinc rod is dipped in
zinc sulphate (ZnSO4) solution and copper rod is dipped in copper sulphate
(CuSO4) solution. The two solutions are separated by salt bridge.
 The two metal rods are then connected externally through ammeter/voltameter
by using wire, the following reactions are observed:

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  At anode, Zinc undergoes oxidation as follows:

(Zn2+ ions go in to the solution and electron flow towards Cu rod)

 At cathode, Copper undergoes reduction as follows:

(Cu2+ ions present in the solution combine with the electrons forming Cu atoms,
which are then deposited on electrode)
 The net chemical change taking place is,

 This is a redox reaction where Zn undergoes oxidation and Cu undergoes

reduction simultaneously.

Emf or Cell potential (Ecell):

The potential difference between the two electrodes of a galvanic cell which causes the
flow of electrons (current) from one electrode to the other is called electromotive force
(EMF).
− EMF of cell is also called as Cell potential.
− The emf of a cell is denoted by Ecell.
− Ecell depends on the nature of electrode, temperature and concentration of the
electrolyte solution.
− Standard emf of a cell is defined as “the emf of a galvanic cell when the reactants and
products of the cell reaction are at unit concentration at 298 K and at 1 atm pressure”. It
represented as E⁰cell

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 E⁰cell = Eright – Eleft
E⁰cell = E⁰cathode - E⁰anode
NOTE:
1. Electrode potential is the potential difference at the interface of metal (electrode)
and solution.
2. Cell potential (Emf) is the potential difference between two electrodes.

NERNST EQUATION
− The electrode potential is calculated by Nernst equation.
− It gives a quantitative relationship between the electrode potential and the
concentration of metal ions.

Consider the following reversible electrode reaction:

𝑅𝑇 [M] 𝑅𝑇 [reduced form]

𝐸 = 𝐸0 − ln 𝐸 = 𝐸 0 − 𝑛𝐹 ln
𝑛𝐹 [Mn+ ] [oxidised form]

Where M = reduced form (product) or

𝑅𝑇 [product]
Mn+ = oxidized form (reactant) 𝐸 = 𝐸 0 − 𝑛𝐹 ln [reactant]

Converting to log,
2.303𝑅𝑇 [M]
𝐸 = 𝐸0 − log
𝑛𝐹 [M n+ ]
But for pure solids (product), [M(s)] = 1
Therefore,
2.303𝑅𝑇 1
𝐸 = 𝐸0 − log
𝑛𝐹 [M n+ ]
By rearranging,
2.303𝑅𝑇
𝐸 = 𝐸0 + log [M n+ ]
𝑛𝐹

R = 8.314 JK-1mol-1 (gas constant)

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T = 298 K These are constant values
F = 96, 500 C/mol
Therefore, applying these values in the above formula,

0.0591
𝐸 = 𝐸0 + log [M n+ ] at 298 K
𝑛

NERNST EQUATION:

2.303𝑅𝑇 1 2.303𝑅𝑇
𝐸 = 𝐸0 − log or 𝐸 = 𝐸0 + log [M n+ ]
𝑛𝐹 [Mn+ ] 𝑛𝐹

0
2.303𝑅𝑇 [anode]
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − log
𝑛𝐹 [cathode]

Where, E = Electrode potential

E⁰ = Standard electrode potential
R = Universal gas constant [8.315 JK-1mol-1]
T = Temperature (in Kelvin, K)
n = number of electrons involved in the redox reaction
F = Faraday constant (96,500 C/mol)
Cell representation:
The electrochemical cell is represented as follows:
− Anode (negative electrode, where oxidation occurs) is written on the left
− Anode is represented by writing metal first and then metal ion, both are separated
by vertical line [M1/M1n+]
− Cathode (electrode where reduction occurs) is written on right hand side
− Cathode is represented by writing metal ion first and then metal, both are
separated by vertical line [M2n+/M2]
− Two half cells are separated by double vertical line, which represents salt bridge

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 M1/M1n+// M2n+/M2
− Concentration and state [solid (s), gas (g), etc] of chemical species are expressed
within the brackets
Example: Cell reaction –

The cell can be represented as,

Fe(s)/Fe(aq)2+// Ag(aq)+/Ag(s)
EMF of this cell can be determined by,
E⁰cell = Ecathode - Eanode
= EAg+/Ag – EFe/Fe2+

NOTE: The potential of individual half cell cannot be measured but only the difference
between the two half cell potentials can be measured which is the emf of the cell.

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Types of Electrochemical cells:

Electrochemical
Cell

Galvanic cell Electrolytic

(Voltaic cell) cell

Chemical Concentration
cell cell

Secondary
Primary cell
cell

1. Electrolytic cell: These are the electrochemical cells which are used to convert electrical
energy to chemical energy.
Eg: Electroplating, electrorefining

2. Galvanic cell:
− Also called as voltaic cell
− Convert chemical energy in to electrical energy

Galvanic cell is further divided in to two types:

I. Primary cells:
− These are the cells which serve as energy source only as long as the active species
are present in the cell.
− The cell reactions are irreversible.
− These are designed for single use; once discharged cannot be charged again.

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 − Eg: Dry cell, Zn-HgO cell, Zn-Ag2O cell, etc.
II. Secondary cells:
− These are the electrochemical cells which can be charged and used.
− The cell reactions are reversible and hence called as reversible cells.
− During discharging, these cells act as voltaic cells by converting chemical energy
in to electrical energy.
− During charging, these cells act as electrolytic cell by converting electrical energy
in to chemical energy.
− Eg: Ni-MH cell (Nickel-metal hydride cell), Lithium-ion cells

Concentration Cell:
It is a type of galvanic cell in which electrode and electrolyte present in both half cells are
same but only the concentration of metal (electrode) or electrolyte is different.

− A concentration cell is made up of two half cells having identical electrodes except
that the concentration of ions at the electrodes are different.
− The half-cell may be joined by salt bridge.
− There is no net cell reaction in concentration cell.
− In galvanic cell, emf arises due to the change in the free energy of the chemical
reaction taking place in the cell. But in concentration cell, emf arises due to the
change in the concentration of either electrolytes or electrodes.
− Eg: Copper concentration cell, Zinc concentration cell, etc.

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“The electrode which is dipped in less concentrated solution (C1) act as anode with lower
potential and undergoes oxidation. The electrode which is dipped in higher concentration
(C2) acts as cathode with higher potential and undergoes reduction”.
Concentration cell is represented as,
M/Mn+(C1)//Mn+(C2)/M

Because both the half-cells are made of same electrode, E⁰cell (standard emf) for
concentration cell is zero. Nernst equation for electrolyte concentration cell is,

0
2.303𝑅𝑇 [M n+ at cathode]
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 + log
𝑛𝐹 [M n+ at anode]
But, E⁰cell = E⁰cathode - E⁰anode = 0
Therefore,
2.303𝑅𝑇 [M n+ at cathode]
𝐸𝑐𝑒𝑙𝑙 = 0 + log
𝑛𝐹 [M n+ at anode]

2.303𝑅𝑇 C2
𝐸𝑐𝑒𝑙𝑙 = log
𝑛𝐹 C1

OR

0.0591 [cathode]
𝐸𝑐𝑒𝑙𝑙 = log at 298K
𝑛 [anode]

REFERENCE ELECTRODE
Definition: Reference electrodes are the electrodes with reference to which the electrode
potential of any other electrode can be measured.
Criteria for an electrode to act as reference electrode:
i. Its electrode potential should be known under the conditions of utility.

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ii. The potential of such electrode should show minimum variation with respect to
temperature.

Types of reference electrode:

I. Primary reference electrode
− Standard hydrogen electrode (SHE) is the only primary reference electrode (gas
electrode).
− Represented as Pt/H2(g)(1 atm)/HCl(1M)
− The potential of SHE is taken as zero by convention. Therefore, potential values of
all other electrodes are expressed w.r.t. this electrode.

Limitations of SHE:
a) Construction and maintenance is difficult since it’s a gas electrode.
b) Pt metal used in the electrode is easily poisoned by any impurity present in the system.
c) Cannot be used in the presence of oxidizing agents like nitrates, H2S, chlorides, etc. as
they poison Pt.
d) Difficulty in maintaining pressure at 1 atm.

II. Secondary reference electrode

Definition: These are the electrodes whose potential is measured w.r.t. SHE and then can
be used as reference electrode for measuring potentials of other electrodes.
Eg: Calomel electrode, silver-silver chloride electrode

Advantages:
a) Easy to set up and operate.
b) Potential values do not vary much with variation in temperature.
c) Not poisoned by oxidizing impurities.

Construction and Working of Calomel Electrode

− Calomel electrode is a secondary reference electrode.
− It belongs to the category of Metal-insoluble salt electrode.

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 − It is also called as Mercury (Hg)-Mercurous chloride (Hg2Cl2).
Construction:

Pt wire

Calomel paste

Mercury
Saturated KCl
Porous disc

− It consists of a glass tube in which pure mercury (Hg) is placed at the bottom.
− It is covered by a paste of Hg and mercurous chloride (Hg2Cl2) which is further in
contact with KCl solution.
− Hg2Cl2 is commonly called as calomel and it is sparingly soluble in water.
− A platinum wire is dipped in the mercury layer, which is used to make electrical
contact with other electrode and to measure potential at the electrode.
− KCl solution used in calomel electrode is of known concentration.
− Electrode potential of the cell depends upon the concentration of KCl used.

Cell representation: Pt, Hg(l), Hg2Cl2(s)/Cl- OR Hg(l), Hg2Cl2(s)/KCl

Working: Calomel electrode can be used as cathode or anode depending upon the nature
of the other electrode of the cell.
The reversible reactions are:

− The electrode reactions are reversible w.r.t. Cl- ions. In other words the potential
of calomel electrode depends on the concentration of chloride ions.

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 − Nernst equation for calomel electrode is given as:

0
2.303𝑅𝑇
𝐸𝑐𝑎𝑙𝑜𝑚𝑒𝑙 = 𝐸𝑐𝑎𝑙𝑜𝑚𝑒𝑙 − log [Cl− ]2
𝑛𝐹

At 298K and n=2, it can be simplified to

𝐸 = 𝐸 0 − 0.0591 log [Cl− ]

Potential value of calomel electrode decreases with increase in KCl concentration
0.1 N KCl E = 0.33 V
1 N KCl E = 0.28 V
Saturated KCl E = 0.24 V

Advantages of Calomel electrode are:

a) Simple to construct
b) Stable
c) Electrode potential value is reproducible

Applications:
a) It is used as secondary reference electrode in the measurement of single electrode
potential.
b) It is the most commonly used reference electrode in all potentiometric determinations.

NOTE: FOR GENERAL UNDERSTANDING

Types of electrodes:
1. Metal-Metal ion electrode
− These electrodes consist of a metal dipped in a solution of its own ions.
− Eg: Zn/Zn2+, Zinc rod dipped in zinc sulphate solution.
Cu/Cu2+, Copper rod dipped in copper sulphate solution.
− These electrodes are reversible with respect to cations.

2. Metal-insoluble salt electrode

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 − Also called as metal-metal salt ion electrode.
− In this electrode, a metal is in contact with its insoluble salt, which is dipped in a
solution of soluble salt having an ion common with insoluble salt.
− Potential arises due to oxidation of metal to its insoluble salt or reduction of
insoluble salt of metal.
− These electrodes are used as secondary reference electrode.
− Eg: a) Calomel electrode: Hg/Hg2Cl2/Cl-
b) Silver-silver chloride electrode: Ag/AgCl/ Cl-
c) Lead-lead sulphate electrode: Pb/PbSO4/SO42-
3. Gas electrode
− In these electrodes, gas (H2 or O2 or Cl2) is continuously bubbled through a
solution of its corresponding ions (OH- or H+ or Cl-) using an inert metal like Pt
or Au.
− Metal provides an electrical contact
− Eg: a) H2 electrode: Pt/H2/H+
b) Chlorine electrode: Pt/Cl2/Cl-

4. Oxidation-Reduction electrode (Redox electrode)

− It is an electrode in which the electrode potential arises due to the presence of
oxidized and reduced forms of the same substance in solution.
− Eg: a) Pt/Fe2+, Fe3+
b) Pt/Ce3+, Ce4+
c) Pt/Sn2+, Sn4+
− Potential arises from the tendency of an ion to change its oxidation state to more
stable one.
− Potential developed is picked up by an inert electrode like platinum.
{Extra Info: The electrolyte solution contains ions of both forms (Fe2+ and Fe3+). Fe3+ is more stable
than Fe2+. Hence, Fe2+ tends to convert to Fe3+ in the solution. This change leads to develop
potential at the electrode}

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5. Amalgam electrode

− Amalgam is the alloy of mercury (Hg).

− Amalgam electrodes are the electrodes in which metal-amalgam (like Pg-Hg) is in
contact with a solution containing its own metal ions.
− Eg: Lead amalgam electrode (Pg-Hg/Pb2+)
Zinc amalgam electrode (Zn-Hg/Zn2+)

6. Ion-selective electrodes (Membrane electrodes)

This is a type of electrode in which membrane is in contact with a solution with which it
can exchange specific ions.
Eg: Glass pH electrode (selective towards H+ ions)

ION SELECTIVE ELECTRODE (ISE)

These are the electrodes which selectively respond to specific ion in a mixture, while
ignoring other ions. The potential developed at the electrode is a function of the
concentration of specific ion in the solution.
− These electrodes are used to measure the concentration of a particular cation or
anion in a mixture.
− The membrane in the electrode is capable of exchanging specific ions with the
solution with which it is in contact.
− ISEs are highly sensitive, selective and suitable for rapid, low cost and accurate
analysis.
Applications:
a) Determination of hardness of water
b) Determination of calcium concentration in milk
c) Nitrate monitoring in waste water
d) Estimation of salinity in sea water
e) Determination of H+ ion concentration

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Glass pH Electrode
− Glass electrode or pH electrode is the electrode which is selective towards H+ ions
in the solution containing a mixture of ions.
− It is used in the measurement of concentration of H+ ions (pH) in the solution.
− When two solutions of different pH values are separated by a thin glass
membrane, there develops a potential difference between the two surfaces of the
membrane.

Construction:

0.1 M HCl

Ag-AgCl electrode

H+ ion

Glass electrode

− Glass electrode is a long glass tube with a glass membrane bulb at the bottom.
− Glass membrane is made up of silicate with composition: SiO2 (72%), Na2O (22%)
and CaO (6%).
− The thickness of glass membrane varies from 0.03-0.1 mm.
− Ag/AgCl electrode is immersed in 0.1 M HCl, is used as internal reference
electrode to measure the boundary potential.
− The metal is also used for making electrical contact with other electrodes.

Cell representation:
Ag(s)/AgCl(s)/HCl(0.1M)/glass membrane

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Working:

− The boundary potential (Eb = E2-E1) arises due to the difference in concentration of
H+ ions inside and outside the glass bulb.
− Boundary potential is given by the equation:
0.0591 [C2 ]
Eb = E2-E1 = log
𝑛 [C1 ]

where C1 and C2 are the concentration of inner and outer acid solutions.

Potential of glass electrode (EG) is sum of three potentials

1) Boundary potential (Eb)
2) Potential of Ag/AgCl electrode (EAg/AgCl)
3) Asymmetry potential (Easym)
[Asymmetry potential is a small potential that exist due to the unevenness in the
membrane and strain on the surface of the membrane]

Electrode potential of glass electrode is given as,

EG = Eb + EAg/AgCl + Easym
Applying the value of Eb in the above equation,
0.0591 [C ]
EG = log [C2 ] + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 + 𝐸𝐴𝑠𝑦𝑚
𝑛 1

0.0591 0.0591 1
EG = log[C2 ] + log + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 + 𝐸𝐴𝑠𝑦𝑚
𝑛 𝑛 [C1 ]

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 0.0591
EG = log[C2 ] + 𝐸𝐺0
𝑛

0.0591 1
Where, 𝐸𝐺0 = log [C ] + 𝐸𝐴𝑔/𝐴𝑔𝐶𝑙 + 𝐸𝐴𝑠𝑦𝑚 and n=1
𝑛 1

EG = 0.0591 log[H + ] + 𝐸𝐺0

We know that pH = -log [H+], Substituting this in the above equation

EG = 𝑬𝟎𝑮 − 𝟎. 𝟎𝟓𝟗𝟏 𝒑𝑯

Determination of pH of a solution using Glass electrode

− The pH of any given solution is measured by a galvanic cell, constructed by
combining glass electrode with standard saturated calomel electrode as reference
electrode.
pH Meter

Calomel Glass electrode

electrode

Solution of
unknown pH

EMF of the above cell i.e. Ecell when immersed in a solution of unknown pH is,
ECell = ECathode - EAnode

ECell = EG - ESCE

Where EG = potential of glass electrode

ESCE = potential of saturated calomel electrode

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ECell = E⁰G - 0.0591 pH - ESCE

Rearranging the equation for pH,

𝑬𝟎𝑮 − 𝑬𝑺𝑪𝑬 − 𝑬𝒄𝒆𝒍𝒍

𝒑𝑯 = 𝑎𝑡 298𝐾
𝟎.𝟎𝟓𝟗𝟏

EG⁰ is determined by constructing a similar cell with solution of known pH.

Advantages of Glass electrode:

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 and biological fluids.
3. The equilibrium is reached quickly.
4. It is simple to operate, gives accurate values of pH.

Limitations of Glass electrode:

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 9 accurately due to alkaline
error.
3. This cannot be used in case of fluoride ions.
Numerical problems on concentration cells
1. A galvanic cell is obtained by combining two Zn electrodes immersed in zinc sulphate
solutions of concentrations 0.05 and 0.25 M at 30 ⁰C. Give the cell representation, cell
reaction and calculate the EMF of the cell.
Solution: Both electrodes in the cell are made of same metal immersed in same electrolyte
solution but of different concentrations. Hence it is an electrolyte concentration cell. Cell
representation is
Zn/ZnSO4 (0.05M)/ZnSO4 (0.25M)/Zn

Cell reaction:

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EMF of the cell:
2.303𝑅𝑇 [M n+ at cathode]
𝐸𝑐𝑒𝑙𝑙 = log
𝑛𝐹 [M n+ at anode]

2.303 𝑋 8.314 𝑋 303 [0.25]

= log
2 𝑋 96500 [0.05]

𝑬𝒄𝒆𝒍𝒍 = 𝟎. 𝟎𝟐 𝑽

2. EMF of the cell Cu/CuSO4 (0.01)//CuSO4 (X)/Cu at 300 K is 0.015 V. Find the
concentration of copper sulphate at cathode.
Solution: EMF of a concentration cell is given by
2.303𝑅𝑇 [M n+ at cathode]
𝐸𝑐𝑒𝑙𝑙 = log
𝑛𝐹 [M n+ at anode]

2.303𝑅𝑇 [Cu2+ at cathode]

𝐸𝑐𝑒𝑙𝑙 = log
𝑛𝐹 [Cu2+ at anode]

Ecell x n x F
[Cu2+ at cathode] = [Cu2+ at anode] x Antilog
2.303 x R x T

0.015 x 2 x 96500
[Cu2+ at cathode] = 0.01 x Antilog
2.303 x 8.314 x 300

[𝐂𝐮𝟐+ 𝐚𝐭 𝐜𝐚𝐭𝐡𝐨𝐝𝐞] = 𝟎. 𝟎𝟑𝟏𝟗 𝑴

3. EMF of the cell Cd/CdSO4 (X)//CdSO4 (0.02M)/Cd at 29 ⁰C is 0.025 V. Find the

concentration of cadmium sulphate at anode.

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Solution: [𝐂𝐝𝟐+ 𝐚𝐭 𝐚𝐧𝐨𝐝𝐞] = 𝟎. 𝟎𝟎𝟐𝟗 𝑴
8. In a spontaneous galvanic cell, M/Mn+(0.03 N) // Mn+(0.064 N)/M develops an EMF of
0.013V at 25 ⁰C. Calculate the valency of metal.
Solution: EMF of a concentration cell is given by
0.0591 [cathode]
𝐸𝑐𝑒𝑙𝑙 = log
𝑛 [anode]

0.0591 [0.064]
0.013 = log
𝑛 [0.03]

0.0591 [0.064]
𝑛= log
0.013 [0.03]

𝒏 = 𝟏. 𝟓

Problems from previous year question papers

1. Calculate emf of a concentration cell constructed by immersing two cadmium
electrodes in cadmium sulphate solutions of concentration 0.1M and 0.75M at 298K. Write
cell representation and electrode reactions.

2. Find the value of X in the concentration cell Cd/CdSO4 (0.0093M)// CdSO4 (XM)/Cd, EMF
= 0.086V at 25 ⁰C and write the cell reactions.

References
1. Basuchandra’s Engineering Chemistry
2. Engineering Chemistry by Jain & Jain
3. Engineering Chemistry: Fundamentals and Applications by Shikha Agarwal

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