Chapter-3

Electrochemistry and applications

1. Introduction
2. Electrochemical cell
3. Electrode potential
4. Nernst equation
5. Electrodes
 Calomel electrode (reference)
6. Batteries
 Leclanche cell
 Lithium ion battery
7. Fuel cells
 H2-O2 fuel cell
 Solid oxide fuel cell
8. Corrosion
 Dry corrosion
 Wet corrosion
9. Factors influencing the rate of corrosion
10. Corrosion controlling methods

1 Engineering Chemistry and Applications Dr. Sivaranjan

 1. Introduction

Electro chemistry is a branch of chemistry which deals with the transformation of electrical
energy into chemical energy or chemical energy into electrical energy. In this, the process of
transformation of chemical energy into electrical energy is highly desired for our day to day
life. Before, we discuss about the important topics, let us learn some of the key definitions.

Conductors: Substances which allow electricity to pass through them are called conductors.
There metals and non-metals as conductors. Based on this, conductors are divided into two
types. a) Metallic conductors and b) Electrolytic conductors

a) Metallic conductors: Conducting nature of these materials is due to the flow of electrons.
These materials do not undergo any chemical change during this process. It does not
involve any transfer of matter. Metals are very good examples of this kind.

b) Electrolytic conductors: Conducting nature of these materials is due to the movement of

ions in a solution. These materials undergo chemical changes during this process. It
involves the transfer of matter. Acids, bases, salt solutions etc. are some examples of this
type of conductors.

Electrolyte: Substances which conduct electricity due to the dissociation into ions in a
solution or fused state are called electrolytes. These are non-metals.

Electrolysis: The process of dissociation of substances by passing electric current through

them in solution or fused state is called electrolysis.

Electrode: Electrode is an electric conductor which makes the contact with non-metallic
parts (electrolytes) of the cell or a circuit. Anode and cathode are the electrodes present in
cells.

Oxidation reaction: Oxidation is the process of loss of electrons by a substance. In this case,
the oxidation state of the element increases from reactants to products (for example, zero to
+2 in the below reaction).
M1 → M12+ + 2e −

Reduction reaction: Reduction is the process of gain of electrons by a substance. In this

case, the oxidation state of the element decreases from reactants to products (for example, +2
to zero in the below reaction).
M 22+ + 2e − → M 2

Redox reaction: Redox reaction is the reaction in which both oxidation and reduction take
place (M1 undergoes oxidation whereas M2 undergoes reduction).

M1 + M 22+ → M12+ + M 2

2 Engineering Chemistry and Applications Dr. Sivaranjan

 2. Electrochemical cell (or) Galvanic cell

Electrochemical cell (or) Galvanic cell is a device in which chemical energy is converted into
electrical energy through a redox reaction. The redox reaction which takes place in this cell is
spontaneous. The following Danial cell is an example of galvanic cell.

Galvanic cell (or) Danial cell

It is made up of two half cells. One is oxidation or anodic half-cell. The other one is the
reduction or cathodic half-cell. The first half cell consists of ‘Zn’ electrode dipped in ZnSO4
solution and second half cell consists of ‘Cu” electrode dipped in CuSO4 solution. Both the
half cells are connected externally by metallic conductor and internally by a ‘salt bridge'.

Salt bridge is a U- tube containing concentrated solution of KCl or KNO3 in Agar-Agar gel
contained porous pot. It provides electrical contact between two solutions.

Anodic half-cell: Oxidation or loss of electrons takes place in the Zn-half cell and it is called
anode.
Zn → Zn 2+ + 2e − (oxidation at anode)

Cathodic half-cell: Reduction or gain of electrons takes place in the Cu-half cell and it is
called Cathode. Here Cu2+ ions accept the electrons which are released by the anodic half-
cell.
Cu 2+ + 2e- → Cu (reduction at cathode)

Finally, the movement of electrons from anodic half-cell to cathodic half-cell produces
current in the Danial cell.

Cell reaction: The overall reaction of the cell is the sum of both the above reactions. The cell
reaction is represented by

3 Engineering Chemistry and Applications Dr. Sivaranjan

 2+
Zn (s) → Zn (aq) + 2e- (oxidation at anode)
2+
Cu (aq) + 2e - → Cu (s) (reduction at cathode)
_______________________________________________
2+ 2+
Zn (s) + Cu (aq) → Zn (aq) + Cu (s) (Cell reaction)
_______________________________________________

Cell representation: Based on the cell reaction, the galvanic or the Danial cell is represented
by the following notation. The oxidation or the anode half-cell must be written on the left-
hand side and the cathode half-cell must be written on the right-hand side. Both the half cells
are separated by a double line (indicates the slat bridge).
+
Zn ( s ) /Zn (2aq 2+
) // Cu ( aq ) /Cu ( s )
(or)
Zn ( s ) /ZnSO 4( aq ) // CuSO 4( aq ) /Cu ( s )

Salt bridge and its significance:

 It is inverted U-shaped porous partition where both the ends are dipped in both the half
cells.
 It is prepared by dissolving gelatin or agar-agar in electrolytes like KCl, KNO3, NH4NO3
etc.
 The above electrolytes are inert to the cell reactions and they do not react with any of the
chemicals inside the cell.
 Over the period of time, accumulation of positive ions (Zn2+) in anodic half-cell and
negative ions (SO42-) in cathodic half-cell takes place. As a result, further oxidation-
reduction process inside the cell slows down or it gets ceased.
 In such cases, salt bridge in the electrochemical cell sends Cl- or NO3- ions to the anodic
half-cell and K+ ions to the cathodic half-cell. Thus, it maintains the electrical neutrality
in both the half-cells to run the cell reactions smoothly.

Though the whole process inside the electrochemical cell (combination of two half-cells) is
well explained as above, questions that have to be answered are the following.
Why should the Zn-electrode loose electrons and Cu-electrode gain electrons in the above
Danial cell? Why not the other way?
To answer these questions, we need to understand the concept of electrode potential.

3. Electrode potential

Introduction: According to the scientist called Nernst, when a metal rod is immersed in a
solution of its salts, there exists two types of force or pressure between the metal rod and the
solution. They are (a) solution pressure and (b) osmotic pressure.
When the solution pressure is greater than the osmotic pressure, metal shows the tendency to
send metal ions into the solution. The result is the loss of electrons or oxidation in that half-
cell.
Thus, metal ions from metal rod run in the solution and the electrons remain on the metal rod.
In this way, the metal rod has negative charge and negative electrode potential.
M ( s ) → M 2 + ( aq ) + 2e −

4 Engineering Chemistry and Applications Dr. Sivaranjan

When the osmotic pressure is greater than the solution pressure, then the solution has the
tendency to send metal ions on to the metal rod (metal ions become metal and accumulate on
rod). The result is due to the gain of electrons or reduction in that half-cell. In this case, the
metal rod has positive charge and positive electrode potential.
M 2+ ( aq ) + 2e − → M ( s )
Thus, the electrode potential of an electrode is defined as the following.

Electrode potential (E):

The potential difference which is developed between the metal and the metallic solution
where a metal (e.g. Zn) is dipped inside the salt solution of its own ions (e.g. ZnSO4) is called
an electrode potential. It is denoted by 'E'.

Electrode potential represents the measure of tendency of metallic electrode to lose or gain
electrons in a half cell when the metal is in contact with the salt solution of its own ions.

In the above diagrams, Zn/Zn2+ half-cell is an example in which oxidation occurs (solution
pressure dominates the osmotic pressure). In this case, Zn-rod sends Zn2+ ions into the
solution and gets negatively charged. In the other case, Cu2+/Cu half-cell is an example in
which reduction occurs (osmotic pressure dominates the solution pressure). In this case,
CuSO4 solution sends Cu2+ ions on to the Cu-metal rod. Here Cu-rod gets negatively charged.

Standard electrode potential (Eo): The electrode potential of an electrode which is measured
when the metal rod is dipped in a salt solution of its own ions having 1M concentration at
298K temperature is called standard electrode potential. It is denoted by 'Eo'.

Therefore, we have the parameter, electrode potential that makes the electrodes to loss or
gain of electrodes. Now, the question is how to measure the electrode potentials. We need to
learn the following.

Standard Hydrogen electrode (SHE): Standard hydrogen electrode is an electrode which is

used as a reference to calculate the electrode potentials of different half-cells. Therefore, the
standard electrode potential of SHE is declared as zero. SHE itself acts as a half-cell. In its
reduction form for example, SHE is represented by
Pt, H (+aq ) / H 2( g )

Standard oxidation electrode potential (Eoox): The standard electrode potential of the half-
cell in which oxidation takes place when it is contact with SHE is called standard oxidation
electrode potential or simply the oxidation potential.

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For example, when the Zn-half cell is connected with the SHE, oxidation takes place in the
Zn-half cell. Here, Zn-electrode acts as anode and SHE is the cathode. The full cell
representation is
Zn( s ) Zn(2aq
+ +
) H ( aq ) H 2( g )
The experimental output of the cell is 0.76 V. It is nothing but the oxidation potential of the
0
Zn-half cell (since, the potential of SHE is zero). EZn Zn(2aq
+ = 0.76 V .
(s) )

Standard reduction electrode potential (Eored): The standard electrode potential of the half-
cell in which reduction takes place when it is contact with SHE is called standard reduction
electrode potential or simply the reduction potential.
For example, when the Cu-half cell is connected with the SHE, reduction takes place in the
Cu-half cell. Here, Cu-electrode acts as cathode and SHE is the anode. The full cell
representation is
H 2( g ) H (+aq ) Cu (2aq
+
) Cu( s )
The experimental output of the cell is 0.34 V. It is nothing but the reduction potential of the
0
Cu-half cell (since, the potential of SHE is zero). ECu 2+
Cu
= 0.34 V
( aq ) ( s)

Note: All the electrodes have both oxidation and reduction potentials and their numerical
numbers are same with a sign difference.
0 0
Eox = − Ered
For example, the oxidation and reduction potentials of Zn-electrode and Cu-electrodes are the
following.
0
EZn Zn 2 +
= 0.76 V ----- oxidation potential
(s) ( aq )

0
EZn 2+
Zn( s )
= −0.76 V ----- reduction potential
( aq )

0
ECu 2+
Cu( s )
= 0.76 V ----- reduction potential
( aq )

0
ECu Cu(2aq
+ = −0.76 V ----- oxidation potential
( s) )

This is how we have to measure the electrode potentials of different electrodes and the data is
preserved as the following.

Electrochemical series:
Standard electrode potentials of different electrodes are measured experimentally w.r.t. the
SHE. The arrangement of carious electrodes based on their standard reduction potentials is
called an electrochemical series. Based on the following series, we can draw the following
conclusions.
 Upper ones (with respect to its lower one) in the given series undergo oxidation (anode)
and act as reducing agents.
 Lower ones (with respect to its upper one) in the given series undergo reduction
(cathode) and act as oxidizing agents.
 All the upper metals can displace the lower metals (metal-metal displacement) from their
salt solutions. For example, zinc displaces copper from its copper sulfate solution in the
Zn-Cu electrochemical cell or Danial cell.

6 Engineering Chemistry and Applications Dr. Sivaranjan

 Li(+aq ) Li( s ) ------- E 0red = −3.04 V Strongest reducing agent
⋮
Zn(2aq
+ 0
) Zn( s ) ------- E red = −0.76 V

⋮ ⋮
Fe(2aq
+
) Fe( s ) ------- E 0red = −0.44 V
⋮ ⋮ 0
Ered increases
H (+aq ) H 2( g ) ------- E 0red = 0.0 V
⋮ ⋮
Cu(2aq
+
) Cu( s ) ------- E 0red = +0.34 V
⋮ ⋮
Ag (+aq ) Ag ( s ) ------- E 0red = +0.80 V
⋮ ⋮
Au(+aq ) Au( s ) ------- E 0red = +1.50 V
Strongest oxidizing agent
⋮ ⋮
F2( g ) F(−aq ) ------- E 0red = +2.85 V

Electro-motive force (EMF) or cell potential (Eocell):

As we know already, a cell is made up of two half cells (anodic and cathodic). The potential
of the total cell at standard conditions (1M, 298K) is nothing but the standard EMF of the
cell. It is the voltage difference between two half cells.

The general cell representation is

Anode half-cell Cathode half-cell

Standard EMF = (Standard reduction potential of cathode) -

(Standard oxidation potential of anode)
0 0 0
Ecell = ERight − ELeft

0
Ecell 0
= Ered( ) Cathode
( 0
− Ered ) Anode

Feasibility of the reaction: The following conditions predict whether the redox reaction is
possible in the cell with the help of electrochemical series.

0
If Ecell = +ve ---- redox reaction is feasible
0
If Ecell = -ve ---- redox reaction is not feasible

7 Engineering Chemistry and Applications Dr. Sivaranjan

Numerical problems based on EMF calculation:

0
Problem-1: Calculate the standard EMF of the following cell where EZn 2+
Zn( s )
= −0.76 V and
( aq )

EH0 + H 2( g )
= 0.0 V . The cell representation is given by Zn( s ) Zn(2aq
+ +
) H ( aq ) H 2( g ) .
( aq )

Answer: Based on the given cell representation, we can write the cell reactions.

2+
Zn (s) → Zn (aq) + 2e- (oxidation)
+
2H (aq) + 2e- → H 2(g) (reduction)
_______________________________________________
+ 2+
Zn (s) + 2H (aq) → Zn (aq) + H 2(g) (redox reaction)
_______________________________________________

Zn-electrode -------- anode

SHE -------- cathode

0
Ecell (
0
= Ered ) Cathode
( 0
− Ered ) Anode
= 0.0 − ( − 0.76)
0
Satandard EMF of the cell = Ecell = 0.76 V
---****---

0
Problem-2: Calculate the standard EMF of the following cell where ECu 2+
Cu( s )
= 0.34 V and
( aq )

EH0 + H 2( g )
= 0.0 V . The cell representation is given by H 2( g ) H (+aq ) Cu(2aq
+
) Cu ( s ) .
( aq )

Answer: Based on the given cell representation, the cell reactions are

+
H 2(g) → 2H (aq) + 2e- (oxidation)
2+
Cu (aq) + 2e- → Cu (s) (reduction)
_____________________________________________
2+ +
H 2(g) + Cu (aq) → 2H (aq) + Cu (s) (redox reaction)
_____________________________________________

SHE -------- Anode

Cu-electrode -------- Cathode

8 Engineering Chemistry and Applications Dr. Sivaranjan

 0
Ecell ( 0
= Ered ) Cathode
( 0
− Ered ) Anode
= 0.34 − (0.0)
0
Standard EMF of the cell = Ecell = 0.34 V
---***---

0
Problem-3: Calculate the standard EMF of the following cell where ECu 2+
Cu( s )
= 0.34 V and
( aq )

0
EZn Zn2 +
= 0.76 V . The cell representation is given by Zn( s ) Zn(2aq
+ 2+
) Cu ( aq ) Cu( s ) .

Answer: Based on the given cell representation, the cell reactions are
2+
Zn (s) → Zn (aq) + 2e- (oxidation)
2+
Cu (aq) + 2e- → Cu (s) (reduction)
_____________________________________________
2+ 2+
Zn (s) + Cu (aq) → Zn (aq) + Cu (s) (redox reaction)
_____________________________________________

Zn-electrode ------ anode

Cu-electrode ------ cathode

0
Ecell ( 0
= Ered )Cathode − ( Ered0 ) Anode
But in the problem, the reduction potential of Zn-electrode is not given. The given one is the
0
oxidation potential, EZn Zn 2 +
= 0.76 V .
When we convert the oxidation potential of Zn-electrode into the reduction potential, it
0
becomes, EZn 2+
Zn
= −0.76 V
0
Ecell (0
= Ered ) Cathode
( 0
− Ered ) Anode
= 0.34 − ( − 0.76)
= 1.11 V
--------------------***----------------------

4. Nernst equation

We must know that the potential of electrodes or half-cells varies with concentration of ions
(solutions) in the cell. Unlike the earlier discussions, we may not have always the standard
conditions with 1M concentration at 298K. Then, the resulting electrode potential deviates
from the standard electrode potential at non-standard conditions. Therefore, we need to find a
way to determine the potentials of half-cells or cells at non-standard conditions as well.

In 1889, Walter Nernst derived a mathematical relationship which enables us to calculate the
half-cell, cell potentials and other parameters at different conditions. The equation is known

9 Engineering Chemistry and Applications Dr. Sivaranjan

as Nernst equation. It basically relates the electrode potential at non-standard conditions (E)
and standard electrode potentials (Eohalf-cell or Eocell) by using the following relation.

2.303RT [products]
E = Eo − log
nF [reactants]

E = Single electrode potential (or) cell potential

E o = Standard single electrode potential (or) standard cell potential
R = gas constant
T = Kelvin temperature
where
n = number of electrons transferred in half-cell reaction
F = Faraday conastant = 96,500 C/mol
[products] = concentration of products
[reactants] = concentration of reactants

Derivation of Nernst equation: Nernst equation calculates the electrode potentials of half-
cells or total cells from the standard electrode potentials. To be specified, it measures the
reduction electrode potentials for instance (oxidation potential = - reduction potential).

Consider the half-cell reduction reaction as the following.

+ −
M (naq ) + ne → M ( s ) (1)

According to the thermodynamics, change in Gibbs free energy (ΔG) under general
conditions can be related to change in standard Gibbs free energy (ΔG0) under the standard
condition for the reaction as
[product]
∆G = ∆G 0 + RT ln (2)
[reactant]
The relation between the change in Gibbs free energy and the electrode potential (E) is
defined as
∆G = − nFE (3)
Under standard temperature and concentrations, the above relation can be extended to the
following form,
∆G 0 = −nFE 0 (4)

Using equations (3) & (4), equation (2) can be written as

[products]
 − nFE = −nFE 0 + RT ln
[reactants]
[M ( s ) ]
 − nFE = −nFE 0 + RT ln n+
[M ( aq ) ]
0 RT 1
 EM n + = EM n+ − ln n+ (for pure solid metal, [M ( s ) ] = 1)
( aq ) M ( s ) ( aq ) M ( s ) nF [M ( aq ) ]

Using the known relation, ln(x) = 2.303log(x), we can write the above equation as

10 Engineering Chemistry and Applications Dr. Sivaranjan

 0 2.303RT 1
EM n + = EM n+ − log n+
( aq ) M ( s ) ( aq ) M ( s ) nF [M ( aq ) ]

On substituting the values of R (8.314 JK-1mol-1), T (298K) and F (96500 C.mol-1), we get
the following final equation.

0 0.0591 1
EM n + = EM n+ − log n+ (5)
( aq ) M ( s ) ( aq ) M ( s ) n [M ( aq ) ]

The above equation is called the Nernst equation for a single electrode (or) half-cell. The
terms 'E and E0' in the above equation are the electrode potential and standard electrode
potentials of half-cells respectively.

The above equation (5) can also be extended for the full cell as well. The full cell reaction
between two electrodes M1 and M2 can be written as
n+ n+
M1( s ) + M 2( aq ) → M1( aq ) + M 2( s )

In this case, the Nernst equation for a complete cell is expressed as

n+
0 0.0591 [M1( aq ) ][M 2( s ) ]
Ecell = Ecell − log n + (or)
n [M 2( aq ) ][M1( s ) ]
(6)
0 0.0591 [M1(n +aq ) ]
Ecell = Ecell − log n +
n [M 2( aq ) ]

The terms 'Ecell and E0cell' in the above equation are the cell potential and standard cell
potentials of a complete cell respectively.

As we have defined already, the standard cell potential E0cell in the equation (6) is expressed
by
0
Ecell 0
= Ered ( )Cathode − ( Ered
0
) Anode
If we clearly observe the Nernst equations of half-cell (equation-5) and complete cells
(equation-6) with the concentration of ions at 1M, they become

At ion concentration = [M n + ] = 1 M,
0
eq.(5)  Ehalf −cell = Ehalf −cell
0
eq.(6)  Ecell = Ecell

It says that at standard condition of 1M concentration, the potentials of half-cells and

complete cells become their corresponding standard potentials without any deviation.

11 Engineering Chemistry and Applications Dr. Sivaranjan

Example problem:
Determine the cell potential of an electrochemical cell made up of Iron and Copper
electrodes. The cell is represented by Fe( s ) Fe(2aq
+ 2+ 0
) Cu( aq ) Cu( s ) where E cell = 0.73 V at 298K
with concentrations [Fe2+] = 0.1M and [Cu2+] = 0.3M.

Answer: Based on the given cell representation, the cell reaction can be written as the
following.
2+ 2+
Fe(s) + Cu (aq) → Fe(aq) + Cu (s)
The number of electrons transferred in the above reaction is n=2.
The Nernst equation for the given cell is written as
0 0.0591 [Fe(2aq
+
)]
Ecell = Ecell − log
2 [Cu (2aq
+
)]
0.0591 (0.1)
= 0.73 − log
2 (0.3)
0.0591  1 
= 1.1 − log  
2 3
0.0591
= 1.1 − (−0.4771) = 0.73 +0.0140 = 0.744
2
Ecell = 0.744 V
-------------------***-------------------

5. Electrodes

Electrode is an electric conductor which is used to make a contact with non-metallic parts
(electrolytes) of the cell or a circuit. Electrodes are commonly used in electrochemical cells.
Electrode is classified as either a cathode or an anode depending upon the reaction that
occurs. If oxidation occurs (loss of electrons) at an electrode, it is called as an anode. If
reduction occurs (gain of electrons), the electrode is known as cathode. Electrodes are good
conductors of electricity and they are made up of different substances with different purposes
in electrochemical cells or batteries. Based on this, electrodes are many in types. We will
discuss about the Calomel electrode as an example of reference electrodes and Glass
electrode (pH) as an example of Ion-selective electrodes.

Electrodes whose electrode potentials are fixed and used to determine the electrode potentials
of unknown electrodes are called reference electrodes. Standard hydrogen electrode (SHE) is
an example of primary reference electrode whose electrode potential is declared as zero.
Since, SHE is difficult to be prepared and maintained, it is usually replaced by other
reference electrodes, which are known as secondary reference electrodes. The electrode
potentials of secondary reference electrodes are measured and fixed with respect to the SHE.
These can be easily prepared and convenient to handle. Calomel electrode and Silver-Silver
chloride electrodes are the examples of this kind. We will talk only about the calomel
electrode.

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A) Calomel electrode (Reference electrode):

Saturated calomel electrode (SCE) or calomel electrode is an example of reference electrode.

It is the mercury – mercurous chloride electrode.

Construction: The calomel electrode consists of a glass vessel having side arm-B, for adding
mercury and other constituents and arm-C, for dipping it in any desired solution. A platinum
wire at 'A' is used for an electrical contact.

It consists of mercury at the bottom over which a paste of mercury-mercurous chloride is

placed. A solution of KCl (or Cl-) is then placed over the paste. A platinum wire sealed in a
glass tube helps in making the electrical contact. The electrode is connected with the help of
the side tube on the left through a salt bridge with the other electrode to make a complete cell.
The calomel electrode is represented by

Pt , Hg / Hg 2Cl2 , Cl(−aq ) (or) Cl(−aq ) , Hg 2Cl2 / Hg , Pt

The role of KCl is to act as a source of chloride ions for the electrode. It also acts as a salt
bridge. It also prevents the electrolyte from coming out and maintains the stable electrode
potential.

Working: Calomel electrode acts as either anode or cathode w.r.to the other electrode
connected to it. When the calomel electrode acts as a cathode, it involves the reduction
reaction. Reduction half reaction results increase in concentration of Cl- ions.

Hg 2Cl2 + 2e− → 2 Hg + 2Cl − (or)

1
Hg 2Cl2 + e − → Hg + Cl −
2
The Nernst equation for the reduction electrode potential of calomel electrode (for the above
reduction reaction) is

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 0 2.303RT
EHg + = EHg + − log[Cl − ]
( s ) Hg ( l ) ( s) Hg( l ) nF
(or )
0
EHg + Hg ( l )
= EHg + − 0.0591 log[Cl − ]
(s) ( s ) Hg ( l )

If it acts as an anode, it involves the following oxidation reaction. Oxidation half reaction
results in fall of concentration of Cl- ions.
2 Hg + 2Cl − → Hg 2Cl2 + 2e−
The potential of the calomel electrode depends upon the concentration of the potassium
chloride (KCl) solution. If KCl solution is saturated, the electrode is known as saturated
calomel electrode (SCE). Then the electrode potential of calomel electrode is 0.24 V.
If the potassium chloride solution is 1 N, the electrode is known as normal calomel electrode
(NCE). Then the electrode potential of calomel electrode is 0.28 V.
If the potassium chloride solution is 0.1 N, then the electrode potential of calomel electrode is
0.33 V.
The electrode potential of any other electrode on hydrogen scale can be measured when it is
combined with calomel electrode. The EMF of such a cell can also be measured. From the
value of electrode potential of calomel electrode, the electrode potential of the other electrode
can be evaluated.

Advantages:
 Easy construction and convenient to handle.
 It is used as a reference electrode in pH measurements.
 Results of cell potential measurements are reproducible.

Disadvantages:
 Solubility of KCl is sensitive to changes in temperature.
 Mercury, mercurous products are toxic and pose greater health hazards.
 Since Hg2Cl2 breaks at 50oC, it cannot be used above this temperature.

Used as a reference electrode in pH measurements:

 The pH meter acts as a voltmeter and measures the potential difference between the
glass electrode (pH electrode) and the reference electrode. Then, the pH will be
measured as the following.

Ecell =ECathode − E Anode

= Ecalomel − Eglass

0 2.303RT
Eglass = Eglass − log[ H + ]
nF
(or )
0
Eglass = Eglass − 0.0591 log[ H + ]
0
 Eglass = Eglass + 0.0591 pH (∵ pH = − log[ H ] )
+

14 Engineering Chemistry and Applications Dr. Sivaranjan

 0
(
Now Ecell = Ecalomel − Eglass + 0.0591 pH )
0
Ecalomel − Eglass − Ecell
 pH =
0.0591

6. Batteries

Battery is a devise in which two or more electric cells are connected with each other in series.
They are used as a source of direct electric current at constant voltage. They can store
chemical energy for later release as electricity. In batteries, chemical energy via redox
reaction is converted into electrical energy.
In general, important characteristics of batteries are: should be with less weight and compact
in size, should provide stable voltage during its use, should provide power for a long time and
should be rechargeable.
Cells that produce an external current are generally called Voltaic cells. The generated
voltage is historically referred to the term “E.M.F” of a cell. Based on the nature of batteries,
they are mainly classified into three types.

A. Primary cells (non-rechargeable cells)

B. Secondary cells (rechargeable cells)
C. Fuel cells

A. Primary cells

 The redox reaction in the cell takes place only in one direction and it is not reversible.
 When all the reactants are converted into products, battery dies and no more electricity as
an outcome.
 The forward redox reaction is generally spontaneous.
 As a result, primary cells cannot be recharged or reused.
 Some common examples are
 Leclanche cell (Dry cell)
 Alkali-metal sulfide cells

i. Dry Leclanche cell (Zn-Carbon cell):

This is an example of primary cells. This cell is also called Zn-carbon cell. This is a dry cell
because electrolytes used in this cell are solids or in the form of paste rather than in liquid
form.

Cell construction:
 This cell contains the cylindrical zinc container in the outer region.
 The central part has the carbon (graphite) rod inside the porous pot which has the
powdered mixture of manganese dioxide and charcoal (carbon).
 The carbon rod containing porous pot is placed in the zinc container without touching the
bottom part of it.
 The gap between the zinc container and the porous pot is filled with the paste of
ammonium chloride and zinc chloride.

15 Engineering Chemistry and Applications Dr. Sivaranjan

 Usage of this paste rather than in liquid form as an electrolyte prevents the leakage. It will
have only enough moisture just to allow current to flow.

Working principle:
 Anode half-cell reaction: Zinc layer in the outer region acts as an anode by undergoing
oxidation.
Zn → Zn 2+ + 2e − (oxidation)

 Cathode half-cell reaction: The carbon (graphite) rod surrounded by a paste containing
manganese dioxide is the cathode. Here, carbon rod is inactive but supports the reduction
of manganese dioxide.
2MnO 2 + H 2O + 2e− → Mn 2O3 + 2OH − (reduction)
2NH +4 + 2OH − → 2NH3 + 2H 2O
2+
Zn 2+ + 2NH3 → [ Zn(NH3 )2 ]
 Cell reaction: The overall cell reaction is a combination of anode half-cell reaction and
cathode half-cell reactions. The EMF of this cell is about 1.4 V.
Zn + 2MnO 2 + 2NH 4+ → [ Zn(NH3 )2 ]2+ + Mn 2 O3 + H 2 O (cell reaction)

 As shown in the above cell reaction, the complete transformation of 'Zn' to [Zn(NH3)2]2+
leads to the dead stage of the battery. Simultaneously, the cell also works only as long as
the paste has the moisture.

Advantages:
 Low cost, large variety of shapes and sizes
 Applications in wide areas
 Portable, orientation flexible and no leakage

Disadvantages:
 Low efficiency under high voltage drains (rapid usage)

16 Engineering Chemistry and Applications Dr. Sivaranjan

 Zinc may get dissolved slowly in NH4Cl and reduces the voltage over the period of time.
 It is not rechargeable.

B. Secondary cells

 Cell reactions are reversible and hence they are called secondary cells.
 The cell reaction is reversed by passing the electric current in the opposite direction
(during charging) to reconstruct the electrodes to their original state.
 These are rechargeable
 Therefore, these are also called Storage or accumulator cells.
 These cells can be used for a large number of times/cycles.
 Some common examples are
 Lithium-ion battery
 Lead-Acid battery
 Nickel-Cadmium (Ni-Cd) battery

i. Lithium-ion battery

Lithium ion batteries are the advanced secondary storage batteries. They exhibit highest
energy density among all batteries. Before studying about these batteries, we must know
about the metal – Lithium (Li).
 It has very low density and therefore it is lighter in weight.
 It has the highest electrochemical potential (standard reduction potential is -3.08 V)
 Lithium metal but directly cannot be used with the traditional aqueous electrolytes due to
vigorous corrosive reaction with water.
 It produces hydrogen gas on reaction with water (exothermic and highly explosive)
1
Li + H 2 O → Li + + OH − + H 2(g)
2
Therefore, Li-ion batteries use Lithium compounds which are more stable than the elemental
Lithium.

Cell construction:
Li-ion batteries mainly consist of anode, cathode, electrolyte and a separator.

Cathode: Lithium metal oxides of general form LiMO2 (metals = M = Co, Ni and Mn) are
used as cathode materials. These are also called intercalation electrodes and they exchange
Li-ions back and forth with anodes during charging and discharging.

Anode: The anode material is a non-metallic compound. Generally, carbon (graphite) is used
as an anode and it stores and exchanges Li-ions with cathode.

Electrolyte: Organic solvents are preferred rather than the aqueous medium in these Li-ion
batteries. Lithium hexafluorophosphate (LiPF6) dissolved in organic solvents like dimethyl
carbonate is used as an electrolyte.

Separator: Separator is a micro-porous layer made up of polyethylene or polypropylene. It

separates both the electrodes and allows only the ions from one electrode to the other
electrode but not electrons.

17 Engineering Chemistry and Applications Dr. Sivaranjan

Working principle:
Li-ion battery is a rechargeable battery due to the reversible reaction. It means the reactants
and products are interconvertible during charging and discharging processes. In this back and
forth mechanism, only the Li-ions move from one electrode to the other through the
electrolyte and separator. Therefore, this operation does not involve the actual oxidation and
reduction but there are electrodes anode and cathode.

Discharging mechanism: During discharging (while using) of the battery, Li-ions move from
the anode (graphite (C)) to the cathode (LiCoO2) through the electrolyte. Simultaneously, the
released electrons flow through the circuit towards the cathode. The forward reaction is the
discharging reaction as shown below.

Charging mechanism: During charging of the battery, Li-ions released by cathode (LiCoO2)
move towards the anode (graphite (C)) through the electrolyte. Simultaneously, the released
electrons flow through the circuit towards the anode. The backward reaction is the charging
reaction as shown below.

The overall EMF of the Li-ion battery is about 3.6 V which is almost three times higher than
Ni-Cd rechargeable battery.

Limitations:
 When the Li-ion batteries are overcharged, it undergoes the following undesired reaction
which involves the over production of Li-ions.

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 LiCoO2 → Li + + e− + CoO2
 When the Li-ion batteries are over-discharged, they undergo the following undesired
reaction to produce Lithium oxide and Cobaltous oxides.
LiCoO 2 + Li + + e − → Li 2O + CoO

Advantages/ Applications:
 They exhibit high energy density compared to the other batteries
 High voltage (around 3.6 v)
 Less damaging towards the environment compared to batteries consisting of cadmium
(Cd), mercury (Hg) etc.
 Large number of charging and discharging cycles.

 They are used in portable electronic devises (cell phones, camera etc.) as power sources.
 Used in electric vehicles (bikes, cars, etc.) for transportation.

Disadvantages:
 These are highly sensitive towards high temperatures and the heat may change the
structure or the shape of the battery.
 Organic solvents in these batteries easily catch fire when leakage occurs and t may lead to
explosion of the battery.
 Over-charging or over-discharging reduces its efficiency and the overall voltage over a
period of time.

7. Fuel cells

 Fuel cell is an electrochemical cell in which the direct conversion of chemical energy into
electrically energy takes place with the continuous supply of reactants.
 In fuel cells, fuels like H2, methanol, etc. are continuously supplied to interact chemically
with oxygen to produce electrical energy. This is a chemical process but not the
combustion.
 Some of the examples of fuel cells are
a) H2-O2 fuel cell (or alkaline fuel cell)
b) Phosphoric acid fuel cell
c) Solid-oxide fuel cell
d) Proton exchange membrane fuel cells

 First two fuel cells belong to the first generation. Third and the fourth one come under
second generation. The present third generation is the hybrid of battery and fuel cells.
 Fuel cells consist of electrolytes sandwiched between two electrodes namely cathode and
an anode.
 One of the electrodes (anode) facilitates the oxidation of the fuel and the other facilitates
the reduction of oxidant (O2). Totally the cell involves a redox reaction.
 Ions generated due to the oxidation and reduction move from either anode to cathode or
vice versa through the electrolyte.
 The electrolytes used on the fuel cells are ionically conductive but electronically neutral.
It means they allow only ions from one electrode to the other electrode.
 The choice of electrolyte also governs the operating temperatures of fuel cells.

19 Engineering Chemistry and Applications Dr. Sivaranjan

 The life time of fuel cells is not exactly known and they continue to work as long as the
fuel is available to the cell.

Advantages of fuel cells:

 Highly efficient compared to other batteries
 Almost zero emission
 Byproducts are less harmful
 No noise or air pollution
 Works as long as the fuel is available
 Sustainable and easily renewable
 Quick charging is possible
 They are useful in wide variety of fields (laptop to power plant)

Disadvantages of fuel cells:

 Initial establishment is costly
 Raw materials are expensive
 H2 fuel production is difficult and costly
 Fuel cell technology is still under developing stage
 Fuel storage may also be a problem and expensive
 They occupy more space compared to other batteries

i. H2-O2 fuel cell (Alkali fuel cell)

 This fuel cell is also called an alkaline fuel cell or hydrogen fuel cell. H2-O2 fuel cell uses
hydrogen gas as a fuel.

20 Engineering Chemistry and Applications Dr. Sivaranjan

Cell construction:
 Both the electrodes (anode and cathode) in this fuel cell are made up of graphite (carbon)
soaked with finely divided Platinum or Palladium (catalyst).
 Aqueous KOH solution is used as an electrolyte.
 The cell contains an inlet on anode side for bubbling H2-fuel and another inlet on cathode
side for bubbling O2 gas.
 The operating temperature range of this fuel cell with an alkaline electrolyte is 60-120℃.

Working principle:
At anode: Hydrogen fuel enters on anode side. Anode facilitates the oxidation of hydrogen
fuel on reaction with the electrolyte, KOH. It results the production of water and electrons.
The produced electrons move towards the cathode through the circuit only.

At cathode: Oxygen enters simultaneously on the other side and comes into contact with the
cathode. Cathode facilitates the reduction of oxygen by making the oxygen to consume the
travelled electrons from anode. It results the hydroxide ions (KOH). Thus, the electrolyte will
never be consumed during the reaction but will be used in the process.

2H 2 + 4OH − → 4H 2O + 4e− (anode)

O 2 + 2H 2O + 4e− → 4OH − (cathode)
−−−−−−−−−−−−−−−−−−−−−−−−−−
2H 2 + O 2 → 2H 2O (cell reaction)

 Thus, the cell works continuously as long as the fuel is supplied.

Advantages/ Applications:
 This fuel cell is used to produce water for Astronauts in space.
 This is the energy source in space vehicles, submarines and army vehicles.
 These are pollution free and an alternative to gasoline powered engines
 High efficiency and they convert 75% of energy source to useful work (it is 25-30% in
other engines)

21 Engineering Chemistry and Applications Dr. Sivaranjan

 Can be operated at low temperatures by using suitable electrolytes.
 Simple byproducts like water.

Disadvantages:
 Costly hydrogen fuel and expensive establishment in the initial stages
 Technology is under developing stage
 Not suitable in all the places
 Storage and transportation of hydrogen is difficult since it is highly flammable.
 Catalysts are expensive

ii. Solid oxide fuel cell (SOFC)

Cell construction:
 Both the electrodes are made up of ceramic substances.
 This fuel cell uses hard, ceramic compounds of metal oxides (like calcium oxide or
zirconium oxide) as electrolytes. Electrolyte is sandwiched between both the electrodes.
 The cell contains an inlet on anode side for bubbling fuel gas (H2+CO) and another inlet
on cathode side for bubbling O2 gas.
 The operating temperature range of this fuel cell with the above electrolytes is around
1000℃.
 The ceramics used in SOFCs do not become electrically and ionically active unless they
reach very high temperatures at around 1000℃.

Working principle:

At anode: Anode facilitates the oxidation of fuel gases (water gas, H2+CO) on reaction with
oxygen ions released from cathode. The reaction results the formation of water and electrons.
Electrons travel through the circuit towards the cathode (to reduce oxygen).

22 Engineering Chemistry and Applications Dr. Sivaranjan

At cathode: Simultaneously, cathode facilitates the reduction of oxygen gas. Here absorption
of electrons (released by anode) and conversion of oxygen into oxygen ions (O2-) takes place.
Oxygen ions travel through the electrolyte towards the anode.

H 2 + O 2− → H 2 O + 2e− (anode)
2− −
CO + O → CO 2 + 2e (anode)
− 2−
O 2 + 4e → 2O cathode)
−−−−−−−−−−−−−−−−−−−−−−−−−−−
H 2 + O 2 + CO → H 2O + CO 2 (cell reaction)

Thus, water gas or other hydrocarbons (CH4) can be used as fuels in this fuel cell.

Advantages/ Applications:
 Low fuel cost
 This fuel cell is operated at high temperature and thus there is no need of catalyst.
 Highly efficient (60%) and can be used in the commercial production
 Uses solid electrolytes and hence no problems regarding the electrolyte management
 Simple byproducts like water, slight heat and low CO2 levels.

Disadvantages:
 Electrolytes are solids but can crack at high temperatures
 High temperatures may lead to corrosion of the cell

8. Corrosion

A. Introduction

The process of slow deterioration or destruction of metals and alloys in the presence of
environment by chemical or electrochemical reaction is called corrosion.

 Corrosion is an irreversible interfacial reaction of metals and alloys with its environment
which results in its consumption or dissolution into the material of a component of the
environment.
 Exclusively physical or mechanical processes such as melting, evaporation, abrasion or
mechanical fracture are not included in the term corrosion.
 Generally metals with low reduction potential undergo corrosion (reduction) easily.

Reasons behind corrosion:

 Metals exist in nature as ores (s oxides, chlorides, sulfides etc.) in their stable forms. The
process of conversion of these ores into pure metals involves the input of energy.
 But, most of the metals are less stable in their pure metallic form than in their ionic form.
Therefore, metals undergo corrosion by returning into their ionic form (oxides,
hydroxides, sulfides are some corrosion products) again easily in environment.

reduction oxidation
(add electrons) (loss of electrons)
Metal ore 
→ Metal 
→ Corrosion products

23 Engineering Chemistry and Applications Dr. Sivaranjan

 Rusting of iron (reddish brown material), corrosion of copper (formation of green film)
etc. are some natural examples.
 Rust is just a type of corrosion and it is the oxidation of iron.

Disadvantages of carrion:
 Metals lose their surface due to corrosion
 Corrosion changes the physical appearance of metals
 Metals lose their properties like conductivity, ductility etc.
 Metals lose their efficiency in different machines
 Regeneration and replacement is expensive and time taking
 Some of the corrosive products are toxic
 Collapse of bridges, accidents of vehicles, failures of machine, loss of human life etc. are
some serious problems.
 The loss due to the corrosion is very huge. It is approximately 3 billion dollars per annum
all over the world.

B. Types or theories of corrosion

Corrosion process can be explained based on the following two main theories.

a) Dry (or) chemical corrosion

b) Wet (or) electrochemical corrosion

a) Dry (or) chemical corrosion

 Dry corrosion occurs when there is no moisture or water to aid the corrosion.
 It occurs by the direct chemical action of the environment/atmospheric gases such as O2,
F2, H2S, SO2 and anhydrous inorganic liquids on the metal surface.
 Dry corrosion occurs in three ways: oxidation corrosion, corrosion by other gases, liquid
metal corrosion.

i. Oxidation corrosion: It is due to the direct action of oxygen in the absence of moisture at
low (or) high temperatures. Oxygen atoms of air are held close to the metal surface by
means of weak Van der Waals forces. They become weak bonds over a period of time
and convert metal into metal oxide.
M → M 2+ + 2e − (oxidation)
O 2 + 2e − → 2O 2− (reduction)
--------------------------------------------------------
M + O 2 → M 2+ + 2O 2− (metal oxide)

The nature of the oxide product on the metal surface plays an important role as it may be
stable, unstable, volatile and porous.

 If a stable product is formed on the surface, it prevents the metal from further corrosion
(Al, Sn, Pb, Cu etc.).

24 Engineering Chemistry and Applications Dr. Sivaranjan

 If the product is unstable, it decomposes readily (Ag, Au, Pt). It is the reason why, these
metals do not get corroded.

 If the product is volatile in nature, it leaves the fresh metal surface. It leads to rapid and
excessive corrosion (Molybdenum oxide).

 If the oxide product is porous, uninterrupted oxidation corrosion takes place (Alkali &
alkaline earth metals).

ii. Corrosion due to other gases: This type of corrosion takes place by the chemical affinity
of gases such as F2, Cl2, H2S, SO2 etc. Iron when attacked by H2S at high temperature
forms a porous 'FeS' layer. Chlorine on silver (Ag) forms a protective layer.

iii. Liquid metal corrosion:

It takes place due to the chemical action of flowing liquid metal on another solid-metal
surface.
It leads to either dissolution of solid metal or internal penetration of liquid metal into solid
metal. Over all, this corrosion weakens the solid metal.
It occurs in devises used for nuclear power. For example, liquid metallic Sodium is used as a
coolant in nuclear devises but leads to corrosion of cadmium rods.

25 Engineering Chemistry and Applications Dr. Sivaranjan

b) Wet (or) electrochemical corrosion

 This corrosion occurs when a conducting liquid is in contact with metal (or) when two
different metals are immersed or dipped partially in a solution.
 This process brings two areas with different potentials in contact with a conducting liquid.
 Thus, it will have anodic area (oxidation) and cathodic area (reduction). Over all, it acts
as an electrochemical cell.
 The metal at anode will be destroyed by oxidation. Hence corrosion always occurs at
anodic area.

Mechanism:
Electrochemical corrosion involves flow of electrons between anodic and cathodic areas.
 At anode, dissolution of metal (corrosion) takes place by forming metal ions

 At cathode, consumption of electrons takes place either by (a) evolution of hydrogen type
or (b) absorption of oxygen type.

Evolution of hydrogen type corrosion occurs when the conducting medium is acidic. For
example, Iron forms ferrous ions and liberates electrons at anode. At cathode, electrons
are absorbed by H+ ions with the evolution of hydrogen gas.

Absorption of oxygen type corrosion occurs when the conducting liquid is neutral
aqueous solution. Cracks developed in iron oxide film cause this type of corrosion. These
cracks develop anodic area. Thus anodic area is small. Remaining iron oxide layer
without cracks acts as cathodic area and it is large usually.

C. Examples of wet corrosion

The corrosion processes which we see in our day to day life can be explained by using the
following example methods. Galvanic corrosion and concentration cell corrosion will be
discussed below.

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i. Galvanic corrosion (Bimetallic corrosion)

• This corrosion takes place when two different metals are connected in a Galvanic cell and
exposed to an electrolyte.
• Metals with low reduction potential have a tendency to form anode (oxidation) and
undergo corrosion.
• For example, in Zn-Cu galvanic cell with their respective salt solution as electrolytes,
Zinc acts as anode (oxidation) and undergoes corrosion. Copper becomes the cathode and
undergoes reduction.

• Oxidation or loss of electrons takes place in the Zn-half cell and it is called anode.
Reduction or gain of electrons takes place in the Cu-half cell and it is called Cathode.
Here Cu2+ ions accept the electrons which are released by the anodic half-cell.
Zn → Zn 2+ + 2e − (oxidation at anode)
2+ -
Cu + 2e → Cu (reduction at cathode)
• The transfer of electrons from anodic half-cell to cathodic half-cell produces current.
The overall reaction of the cell is the sum of both the above reactions. The cell
reaction is represented by
2+ 2+
Zn (s) + Cu (aq) → Zn (aq) + Cu (s) (Cell reaction)

• In the above cell, the reduction potential Zinc (-0.76 V) is less than Copper (+0.34 V).
Thus, the metal with lower reduction potential always undergoes oxidation/corrosion
with respect to the other metal with higher reduction potential.
• Based on the electrochemical series, when 'Fe' (-0.44V) is connected to 'Zn' (-0.76V),
zinc undergoes oxidation/corrosion (anode). Similarly, when 'Cu (+0.34V)' is
connected to 'Ag (+0.80V)', copper undergoes oxidation/corrosion (anode).

27 Engineering Chemistry and Applications Dr. Sivaranjan

ii. Concentration cell corrosion

Type-1:
 This corrosion takes place when a same metal is exposed to different oxygen
concentrations in the environment.
 When Zn-rod is partially immersed in neutral salt solution, the metal portion inside the
electrolyte is less oxygenated than the portion above the electrolyte.
 Due to this, potential difference is created and it causes the flow of electrons from less
oxygenated area to more oxygenated area. So, it is an example of concentrated cell
 Less oxygenated Zn-rod portion inside the solution become anodic and gets corroded.

Zn → Zn 2+ + 2e − (Less oxygenated part - anode)

1
O + H 2O + 2e − → 2OH − (more oxygenated part - cathode)
2 2

Type-2:
 Cracks, cavities and pinholes on the protective film (metal oxide) developed on the metal
surface cause this kind of corrosion (pitting corrosion).
 Cracks, cavities and pinholes are small areas and are less oxygenated. So, they act as
anodes.
 Remaining normal area of the metal is large in area and is more oxygenated and it acts as
a cathodic area.
 Due to the potential difference between these two areas, flow of electrons takes place
from anodic to the cathodic area through atmospheric moisture medium.

Fe → Fe 2+ + 2e − (Less oxygenated part - anode)

1
O 2 + H 2O + 2e− → 2OH − (more oxygenated part - cathode)
2

28 Engineering Chemistry and Applications Dr. Sivaranjan

 Type-3:
 This corrosion (Crevice corrosion) takes place to the metal under insulated areas
(insulated by sand, duct, rubber etc.).
 Metal under the insulated area is less oxygenated compared to the metal which is outside.
 Therefore, less oxygenated metal portion acts as anode, undergoes oxidation and
corrosion. More oxygenated metal portion (which is not insulated) acts as cathode.

29 Engineering Chemistry and Applications Dr. Sivaranjan

  Differences between dry and wet corrosions:

Dry (or) chemical corrosion Wet (or) electrochemical

corrosion
It takes place in dry condition It takes place in wet condition in
presence of electrolytes
It involves the direct chemical It involves the formation of a large
attack of environment on the metal number of galvanic cells
Corrosion product accumulates at Corrosion takes place at anode but
the same place where it is taking accumulates at cathode
place
Uniform corrosion takes place Non-uniform corrosion takes place

9. Factors influencing the rate of corrosion

The nature and the rate of corrosion depend upon both metal and the environment. Therefore,
we have to study about the influencing factors from both sides.

 Nature of metal

i. Purity of metal:
 Lesser the percentage purity of metal, faster is the corrosion.
 Impurities in metals cause heterogeneity. It forms tiny electrochemical cells at the
exposed parts and corrosion takes place at anodic parts (around the impurity).

ii. Physical state of metals:

 Metals with small grain size (more solubility) have more tendencies to undergo
corrosion.
 Stressed/strained parts of metals also easily undergo corrosion.

iii. Electrode potential:

 Based on the electrochemical series, metals with lower electrode reduction potential
readily undergo corrosion.
 For example, Zinc undergoes faster corrosion compared to Cu, Ag, Au, Pt etc.

iv. Relative areas of cathode and anode:

 The rate of corrosion of metal is more when the cathode area (reduction) is more than the
anodic (oxidation) area.
 Larger cathode area leads to rapid consumption of electrons (reduction) liberated from
anode and it enhances the anodic oxidation. In such a way, it enhances the corrosion at
anode.

v. Products of corrosion:
 If the produced corrosion product is porous, volatile and soluble, it further enhances the
corrosion (Fe, Zn, Mg etc.)

30 Engineering Chemistry and Applications Dr. Sivaranjan

 If the corrosion product is stable, unstable, non-porous and insoluble, it prevents the
metal from further corrosion (Cu, Ag, Au, Pt etc.).

 Nature of environment

i. Temperature:
 As temperature increases, the rate of corrosion also increases. This is due to the faster
electrochemical reactions at higher temperatures.

ii. Humidity in air:

 The humidity/moisture in atmosphere provides water to the electrolyte and helps to set
up electrochemical cells. The formed metal oxide film absorbs moisture and creates
electrochemical cells further.
 Therefore, as humidity/moisture increases, rate of corrosion also increases.

iii. Effect of pH:

 As the pH of the medium/electrolyte decreases, it becomes more acidic. More the acidic
nature of electrolyte, higher is the corrosion (evolution of hydrogen type).

iv. Impurities in atmosphere:

 Impurities such as F2, H2S, SO2, acid fumes, suspended particles etc. in industrial areas
increase the rate of corrosion (corrosion by gases other than oxygen).

v. Percentage of oxygen in atmosphere:

 As the oxygen percentage in atmosphere increases, the rate of corrosion also increases.
 The presence of more and less oxygenated electrode areas leads to the oxygen
concentration cell corrosion.
 The corrosion of the metal occurs at the anodic parts (less oxygenated area).

10. Corrosion control methods

Corrosion controlling methods are techniques used to minimize corrosion such as the
application of anti-corrosion coating, cathodic protection or other methods that make metal
resistant to corrosion.

Corrosion control methods

Cathodic protection Metal coatings

1. Sacrificial anode method Electro-plating

2. Impressed current method

31 Engineering Chemistry and Applications Dr. Sivaranjan

Having a good understanding of the conditions, which contribute to corrosion, can prevent
corrosion. Making the right decision in the kind of metal to use could also lead to a
significant reduction in terms of corrosion. Some of the important corrosion control methods
are discussed below.

A) Cathodic protection

In an electrochemical cell or in nature, one of the metal electrodes undergoes corrosion by

self-oxidation. In this case, it behaves as an anode. Therefore, as we know already, corrosion
takes place only at anodes. If the corrosion takes place on a base metal that we are interested
in (using for some purpose), then it needs to be protected.
The method of protecting the base metal by making it to behave like a cathode is called
cathodic protection.
There are two types of cathodic protection methods:
 Sacrificial anode method
 Impressed current method

i. Sacrificial anode method:

 In this method, the base metal (metal to be protected) is connected to another metal whose
reduction potential is less than the base metal.
 Due to this, the metal with low reduction potential behaves like an anode (undergoes
oxidation) and makes the base metal to behave like a cathode.
 In this manner, all the corrosion is concentrated at the new anodic metal and the base
metal is safe.
 Since, the new anodic metal is sacrificed to protect the base metal, it is called the
sacrificial anode and method is named as the sacrificial anode method.
 The sacrificial anode will be completely corroded after a point of time and it has to be
replaced by a fresh one again.
 Commonly used sacrificial anode metals are Zn, Mg, Al, and their alloys. These metals
generally possess low reduction potentials.

Applications:
 Sacrificial Anodes are used to protect the hulls of ships, water heaters, and pipelines,
tanks above the ground, underground tanks, and refineries.

32 Engineering Chemistry and Applications Dr. Sivaranjan

ii. Impressed current method:

 In this method, current from an external source is applied in the opposite direction
(impressed) to nullify the corrosion current.
 This is useful to convert a corroded base metal anode into a cathode. Consequently, it
protects the base metal from further corrosion.
 The common anode materials used here are inert materials like graphite or the one, which
deteriorates. They are replaced periodically.
 This method is used when electrolyte resistivity and current requirements are high.
 It is suitable for large structures and in case of long-term applications.
 This method is more effective when compared to the sacrificial anode method.
Applications: This method is employed in case of buried structures such as pipelines, tanks,
marine piers and laid-up ships etc.

The main difference between sacrificial anode and impressed current methods is that the
sacrificial anode system relies on the difference in potential between the anode and the base
metal (structure), whereas the impressed current system uses an external power source to
drive the current.

33 Engineering Chemistry and Applications Dr. Sivaranjan

B) Electroplating (Ni-electroplating)

 Electroplating method is an application of surface coatings to control the corrosion of

important base metals or structures.

 Electroplating is the process of depositing a layer of one kind of metal upon another
metal/non-metal by means of electrolysis to prevent the corrosion of metals or for
decorative purposes. It is basically a form of electro-deposition.

 This method involves the passage of direct current (DC) from external source through the
electrolyte.
 Before electroplating, the base metal (to be protected/coated) is subjected to acid pickling
to remove any scales, oxides, and oils from its surface.
 In this method, the base metal is made as cathode and the metal used to coat the base metal
is made as anode. Here anode metal is the coating metal.
 Both the electrodes are dipped in the electrolyte solution, which contains the ions of the
anode metal.
 When the DC is passed, the anode metal is soluble in electrolyte and its ions migrate
towards cathode. The metal ions become metals due to reduction at cathode and get
deposited over the surface of base metal as a thin layer.

Nickel electroplating:

 Nickel plating is similar to other electroplating processes that employ soluble metal
anodes.
 In this process, Ni-metal is the anode and it is used to coat another metal or a non-metals
(object). Here the object acts as a cathode.
 Both the electrodes are connected to DC supply and they are immersed in a conductive,
aqueous Nickel sulfate electrolyte.
 The flow of direct current causes the Ni-metal anode to dissolve and the other electrode
(the cathode) to become covered with nickel.

 At anode: When current flows, metallic nickel is dissolved to form divalent positively
charged ions (Ni2+), enter the Nickel salt solution and flow towards the object to be coated
(cathode). This oxidation at anode releases two electrons and they flow towards the
cathode via the circuit.
Ni → Ni2+ + 2e − (At anode)

34 Engineering Chemistry and Applications Dr. Sivaranjan

 At cathode: The positive Ni-ions react with two electrons and get converted to metallic
nickel (Ni0) at the cathode surface.
Ni2+ + 2e − → Ni (At cathode)

Required conditions for Ni-electroplating:

 Temperature is 40-70°C
 Current of 20-30 mA/cm2
 At the pH usually 4.5 to avoid the formation of Nickel hydroxide
 Organic compounds as additives (example: Benzopyrone)

Uses of Ni-electroplating:
 Nickel layers on metal or non-metallic objects are decorative
 It provides resistance to corrosion of metals
 Ni-plating is an undercoat for the chromium plating.

Factors influencing the electroplating method

 Oxides, scales, oils etc. accumulated on the base metal affect the bright and smooth
coating. Cleaning the base metal prior to electroplating is compulsory.
 Concentration of metal ions in the electrolyte affects this process. Low concentration will
produce uniform metal coating.
 Electrolyte or the metal ion solution should not interact chemically with the base metal.
 Low or medium temperatures result uniform coating
 Additives like glue will make the coating strong.

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35 Engineering Chemistry and Applications Dr. Sivaranjan