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ELECTROCHEMISTRY AND
CORROSION ENGINEERING
MODULE 2
 ELECTROCHEMISTRY AND CORROSION ENGINEERING

MODULE-2

Basic terminology, Nernst Equation, Electro chemical series, Electrodes, Concentration cells,
Theories of corrosion, Types of Corrosion, Factors influencing corrosion, Corrosion control
methods, Surface coatings.

MODULE-2
 ELECTROCHEMISTRY AND CORROSION ENGINEERING

Lecture-10
Basic Terminology, Nernst Equation
Electrochemistry is the branch of chemistry which deals with the transformation of electrical energy
into chemical energy and vice−versa. It is the study of phenomena at electrode solution interfaces.

Conductance:
The passage of electricity through a substance is called electrical conductance. Electrical conductance
involves movement of electrons or ions. A substance which allows electric current to pass through it,
is called a conductor.
Ex: All metals fused salts, acids, alkalis.
The electrical conductors are of two types,
1. Metallic or Electronic conductors
2. Electrolytic conductors
1. Metallic or Electronic conductors:-
In a solid, the electrical conduction involves the free movement of electrons in the metallic lattice,
without any movement of the lattice atom, ie atomic nuclei remain stationary. This type of
conduction is called metallic conduction. Metallic conductors are further sub classified into three
types.
i. Good conductors
ii. Semi-conductors
iii. Non-conductors or Insulators
(i) Good conductors:- It is a substance, which conduct electricity fully and freely.
Ex:-Metals like Cu, Al and Fe
(ii) Semi-conductors:- A substance, which partially conducts electricity.
Ex:-Silicon, Germanium.
(iii) Non-conductororInsulators:-It is a substance, which does not conduct electric current i.e., which does
not allow the passage of current through it.
Ex:- Wood.
2. Electrolytic conductor:-
It is a substance, which in aqueous solution or in molten state liberates ions and allows electric
current to pass through. Electrolytic conductors are further sub classified into three types depending
upon the extent of dissociation at ordinary dilutions.
• Strong electrolytes:- These are completely dissociated into ions at all concentrations.
Ex:- NaCl, HCl, NaOH, etc.
• Weak electrolytes:-Weak electrolytes dissociate only to a small extent even at very high dilutions.
Ex:- CH3COOH, NH4OH,etc.
• Non-electrolytes:-Non-electrolytes do not dissociate into ions even at low dilutions.
Ex:-Glucose, Sugar.

Conductivity of Electrolytes:-
Electrolytic conduction involves the transfer of electrons through the migration of positive and
negative ions towards the electrodes. In an ionic solution, the cations and the anions are free to
move and both can transport charge. When a current is passed through the solution, the ions carry
a current. The ability of the ions in solution to carry current is conductivity. The conductivity of a

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solution depends on the number of anions and cations present in it and also on how readily these
ions can move.
Differences between Metallic and Electrolytic conductors:-
[Link] Metallic conductors Electrolytic conductors
1. It involves the flow of electrons in a It involves the movement of ions in a solution.
conductor.
2. It does not involve any transfer of matter. It involves transfer of electrolyte in the forms
of ions.
3. Generally metallic conduction shows an But the resistance of an electrolytic solution
increase in resistance as the temperature is decreases as the temperature is raised.
raised.
4. No net chemical change takes place. Chemical reaction takes place at the two
electrodes.

Redox Reactions:-
Those reactions in which both oxidation and reduction reactions takes place are known as redox
reactions.
Oxidation:-
Oxidation is a process which involves loss of electrons by a substance.
Zn(s) Zn2+(aq) + 2 e─ ................................................. Oxidation
Reduction:-
Reduction is a process which involves gain of electrons by a substance.
Cu2+(aq) + 2 e─ Cu(s) ............................... Reduction

Oxidation and reduction must always go side-by side. Thus if we place Zn metal in a solution of
CuSO4, immediate preparation of Cu takes place.
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

In this change, the Zn atom is oxidized to Zn ion (Zn+2), since it loses electrons, while the copper ion
(Cu+2) is reduced to copper atom, since it gains electrons.
Zn(s) Zn2+(aq) + 2 e-...................................Oxidation
2+
Cu (aq) + 2 e Cu(s) - ................................................. Reduction
2+
Zn(s) + Cu (aq) Zn2+(aq) + Cu(s) .................Redox

The overall reaction obtained by adding the oxidation and reduction reactions is called redox
reaction.

Electrode Potential:-
When a metal is placed in the solution of its own salt, a difference of potential is, consequently set
up between the metal and the solution. At equilibrium, the potential difference between the metal

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and the solution becomes a constant value. This is known as Electrode potential of the metal. In
other words, the tendency of an electrode to lose or gain electrons, when it is in contact with its
own ions is known as Electrode potential.
A metal (M) consists of metal ions (Mn+), with the valency electrons that bind them together. If a
metal is in contact with a solution of its own salt, the positive ions in the metal come into
equilibrium with those in the solution, leaving behind an equivalent number of electrons on the
metal. Thus, the metal acquires a negative charge, since it is now left with excess number of
electrons and a number of positive metallic ions are formed in solution. If the positive metallic ions,
from the solution, enter the metallic lattices, then metal acquires a positive charge.
• The measure of tendency of a metallic electrode to lose or gain of electrons, when it is in contact
with a solution of its own salt of unit molar concentration at 25℃.
• The tendency of an electrode to lose electrons is a direct measure of its tendency to get oxidized
and this tendency is called oxidation potential.
• The tendency of an electrode to gain electrons is a direct measure of its tendency to get reduced,
and this tendency is known as reduction potential.
The value of reduction potential is negative of its oxidation potential and vice versa. Thus if the
oxidation potential of an electrode is +X volts, then its reduction potential will have a value of –X
volt.

Single Electrode Potential:-

The potential generated when a metal rod is dipped in the aqueous solution of its salt or a gaseous
non-metal in contact with a solution containing its anion in the form of salt (or acid or alkali) (which
functions as single electrode) is called single electrode potential(E).
Ex: Metal electrodes like Zn electrode Zn/Znaq +2, copper electrode Cuaq+2/Cu etc and non-metal
electrodes like Hydrogen electrode, H+(aq)/H2(g), Pt, Chlorine electrode, Pt; Cl2 (g)/Cl(aq)-, Pt etc.
The value of this potential depends on the chemical identity of the metal or non-metal, the
concentration of the concerned ion in the aqueous solution and temperature.

Standard Electrode Potential:-

The potential exhibited by a single electrode at unit concentration of the concerned metal ion or
non-metal ion solution at 25℃ is called standard electrode potential (Eo)

Electrochemical Cells:-
The devices that are used to convert the chemical energy produced in a redox reaction into
electrical energy or vice versa are known as an Electrochemical cells. The electrode where oxidation
occurs is called anode, while the electrode where reduction occurs is called cathode.
An electrochemical cell is classified into two types a) Electrolytic cells and b) Galvanic cells (voltaic
cells).
The devices in which chemical changes occur in the presence of applied electrical energy are called
Electrolytic cells. The devices in which electrical energy is generated from chemical energy,
produced due to chemical reactions, are called Galvanic cells.
Galvanic Cells:
Galvanic cells are further divided into two types- chemical cells and concentration cells.
Ex: Daniel cell
Daniel cell:-
Daniel cell consists of Zn electrode, dipped in ZnSO4 solution (where oxidation takes place) and a
copper electrode, dipped in CuSO4 solution (where reaction takes place). Each electrode may be

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regarded as a half- cell. The two solutions are separated by a salt bridge which helps them to seep
through, and come in contact with each other automatically.
The electrode reactions in Daniel cell are

The tendency of Zn to form Zn+2 is greater than the tendency Zn+2 to get deposited as Zn and hence,
Zn metal acquires a negative charge. On the other hand, tendency of copper to go into solution is
less than the tendency of Cu+2 to get deposited as Cu and hence, copper electrode becomes
positively charged. The EMF of the cell is 1.1 volts.

Representation of a Galvanic Cell:-

1. Anode is written on the left-hand side, while cathode is written on the right-hand side.

2. The electrode on the left (i.e Anode) is written by writing the metal (or solid phase) first and then
the electrolyte. The two are separated by a vertical line or a semicolon. The electrolyte may be
represented by the formula of the whole compound or by ionic species. Additional information
regarding concentration may also be mentioned in bracket.
Representing anode half- cell:
Zn/Zn+2 or Zn: Zn+2 or Zn; ZnSO4 (1M); Pt, H2 (1atm); H+ (1M)
3. The cathode of the cell is written on the right-hand side. In this case, the electrolyte is represented
first and the metal (or solid phase) thereafter. The two are separated by a vertical line or a
semicolon.
Representing cathode half- cell:
Cu+2/Cu or Cu+2; Cu or Cu+2(1M); Cu or CuSO4 (1M)/Cu

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4. A salt bridge is indicated by two vertical lines, separating the two half-cells. Thus, applying above
consideration to Daniel cell, we may represented as
Nernst Equation:-
The Nernst Equation is
2.303RT Products
E = E0 ─ log [ ]
nF Reactants

E – Electrode potential R – Gas constant

E0 – Standard electrode potential T – Temperature
n – Number of valency electrons F – Faraday (96,500 coulombs)

Derivation of Nernst Equation:-

Consider a general reversible reaction
Mn+(aq) + ne- M(s)
For a reversible reaction, the free energy change (ΔG) is given as
[product]
ΔG = ΔG0 + RT ln ..…….1
[reactant]
where ΔG0 is known as the standard free energy change (i.e., the change in free energy, when the
concentrations of the reactants and the products are unity each). The above equation, is known
popularly as Van't Hoff reaction isotherm.
In a reversible reaction, the electrical energy is produced due to free energy decrease, i.e
−ΔG = nEF and ΔG0 = −nE0F
Substituting ΔG & ΔG0 values in equation (1)
0 [M]
−nEF = −nE F + RT ln [Mn+ ]
0 1
−nEF = −nE F + RT ln[Mn+ ]
we have
−nFE = −nFEo + RT ln Q ........................................ 2
Divide both sides of equation 2 by −nF, we have

E = Eo − (RT/nF) ln Q............................................. 3
Equation 3 can be rewritten in the form of log10
E = Eo − (2.303RT/nF) log10Q .................................4
For a cell reaction M(s) + Nn+(aq) Mn+ (aq) + N(s)
[𝑴𝒏+][𝑵] [𝑴𝒏+]
O= [𝑴][𝑵𝒏+]
=
[𝑵𝒏+]
Then equation 4 can be written as
𝟎.𝟎𝟓𝟗𝟏𝟔 [𝑴𝒏+]
E = Eo − log 10
[𝑵𝒏+]
𝒏
Applications:
The Nernst equation can be used to calculate:
• Standard electrode potentials
• Comparing the relative ability as a reductive or oxidative agent.
• EMF of an electrochemical cell
• Unknown ionic concentrations
• The pH of solutions and solubility of sparingly soluble salts can be measured with the help of the
Nernst equation

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Lecture-11
Electrochemical series, Concentration cells

Electrochemical Series:-
The electrochemical series is built up by arranging various redox equilibria in order of their standard
electrode potentials (redox potentials). The most negative E° values are placed at the top of the
electrochemical series, and the most positive at the bottom.
The electrochemical series
Equilibrium E° (volts)

-3.03

-2.92

-2.87

-2.71

-2.37

-1.66

-0.76

-0.44

-0.13

+0.34

+0.80

+1.50
Importance of Electrochemical Series:
1. The metal which is higher in electrochemical series acts as reducing agent (or) anode and undergoes
corrosion first.
2. Metals above hydrogen are called active metals, which can displace hydrogen from dilute acids or
water.
Eg:- Zn + 2HCl ZnCl2 + H2
3. The metals below hydrogen are less reactive. They do not liberate H2 from dilute acids and water.
4. The metal with higher negative potential displaces a metal with lower negative potential or positive
potential (i.e., all metals below it in the series) from the salt solution of the metal.
Eg:- Zn displaces all metals underneath it in the electrochemical series.

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Zn + CuSO4(aq) ZnSO4 (aq) + Cu

5. The reactivity (or) reducing character decreases from top to bottom of electrochemical series. So, Li is
the strongest reducing agent and fluorine is the strongest oxidizing agent.
Application of Electrochemical Series:-
1. Oxidizing and reducing strengths: Electrochemical series helps us to identify a good oxidizing
agent or reducing agent.
2. Used for calculation of standard EMF (E0) of electrochemical Cell.
3. Useful for predicting the feasibility of redox reaction.
4. Useful for predicting the product of electrolysis

Differences between Electrochemical Series and Galvanic Series:-

[Link] Electrochemical series Galvanic series

1 It is based on the electrode potential values It is based on the corrosion potential in

measured in standard condition. sea water.
2 Standard electrode potential is a constant Corrosion potential varies from
value. environment to environment.
3 Metals and non-metals are included but not Metals and alloys are included
alloys.
4 It indicates the relative oxidizing/reducing It indicates the relative corrosion
tendency. tendency.
5 The position of the metal or non-metal is The position of the metal or alloy varies
fixed. with the environment.

Problems:

1. Find the potential of a half cell at 298K for a cell FeSO4(0.1M)/Fe, standard electrode potential
being -0.44V.
Sol: The Nernst equation for the given conditions can be written as follows;
EFe2+/Fe = Eo – [(2.303RT)/nF] x log 1/[Fe2+]
= Eo – 0.0591/n x log 1/[Fe2+]
Here,
E° = -0.44 V, n = 2, [Fe2+] = 0.1 M
E = -0.44 – [0.0591/2 x log 1/[0.1]]
= -0.44 – 0.0295
= – 0.4695V

2. What is the cell Potential of the electrochemical cell in which the cell reaction is: Pb2+ + Cd → Pb
+ Cd2+; given that Eocell = 0.277 volts, temperature = 25oC, [Cd2+] = 0.02M, and [Pb2+] = 0.2M.
Sol: Here, two moles of electrons are transferred in the reaction. Therefore, n = 2
The reaction quotient (Q) is given by [Cd2+]/[Pb2+] = (0.02M)/(0.2M) = 0.1.
The temperature is equal to 25oC, the Nernst equation can be written as follows;
Products
Ecell = E0cell – (0.0592/n) log[ ]
Reactants
The equation can now be rewritten as:
Ecell = 0.277 – (0.0592/2) × log(0.1)

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= 0.277 – (0.0296)(-1)
= 0.3066 Volts
Thus, the cell potential of electrochemical cell at a temperature of 25oC is 0.3066 volts.

where 𝑐1 and 𝑐2 are the concentrations of active metal ions [𝑀n+] in contact with two electrodes
respectively and 𝑐2 > 𝑐1. Also
𝐸0 = 𝐸0cathode − 𝐸0anode = 0

Therefore
𝐸 =−
2.303 RT
log
c1 (𝑜𝑟) 𝐸 =
2.303 RT
log
c2 (or) 𝐸 =
0.0592 V
log
c2
cell nF c2 cell nF c1 Cell n c1

Concentration Cells:
A cell in which both the electrodes are of the same type but the solutions of electrolyte in which they
are inserted have different concentration is called concentration cell. In concentration cells electrical
energy is produced from the transfer of a substance from the solution of a higher concentration to
solution of lower concentration.

Concentration cell is made up of two half-cells having identical electrodes, identical electrolyte, except
that the concentrations of the reactive ions at the two electrodes are different. The two half-cells may
be joined by a salt bridge.

Theory:-
When a metal (M) electrode is dipped in a solution containing its own ions [Mn+], then a potential is
developed at the electrode, the value of which varies with the concentration(c) of the ions in
accordance with the Nernst equation.
2.303 RT 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠
𝐸 = 𝐸0 − log [ ]
nF 𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
The overall reaction is

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Ag(c2) Ag(c1)
In general : 𝑀 (𝑐2)
n+
𝑀n+(𝑐1)

In this cell, the following reactions occur:

At left electrode(anode): 𝑀 𝑀n+(𝑐1) + 𝑛𝑒–
At right electrode (cathode): 𝑀 (𝑐2) + 𝑛𝑒
n+ –
𝑀
The EMF developed is due to the transference of metal ions from the solution of higher concentration
(𝑐2) to the solution of lower concentration (𝑐1).
2.303 RT 𝑐1
𝐸 = 𝐸0 − log [ ]
nF 𝑐2

where 𝑐1 and 𝑐2 are the concentrations of active metal ions [𝑀n+] in contact with two electrodes
respectively and 𝑐2 > 𝑐1. Also
𝐸0 = 𝐸0cathode − 𝐸0anode = 0

Therefore
𝐸 =−
2.303 RT
log
c1 (𝑜𝑟) 𝐸 =
2.303 RT
log
c2 (or) 𝐸 =
0.0592 V
log
c2
cell nF c2 cell nF c1 Cell n c1

Types of Concentration Cells:

There are two types of concentration cells,
1. Electrode concentration cells
In these cells, two like electrodes at different concentrations are dipped in the same solution.
2. Electrolyte concentration cells
In these cells, the two electrodes of the same metal are dipped in solutions of metal ions of different
concentrations, due to which a difference in the potential at the electrode and the electrolyte
solution in which it is dipped.

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Lecture-12
Electrodes

Electrodes are used to measure conductivity.

Reference Electrodes:-
The electrode of standard potential, with which we can compare the potentials of another
electrodes, is called a reference electrode. It is an electrode which has a stable and well-known
electrode potential.
Types of Electrodes:
• Standard Hydrogen Electrode
• Calomel Electrode
• Glass Electrode

Calomel Electrode:-
It is the most commonly used mercury- mercurous chloride (Hg2Cl2) electrode. The potential of the
calomel electrode, on the hydrogen scale, has been found to vary with the concentration of the
potassium chloride solution used. The potential of this electrode is equal to the EMF of the cell.
Diagram:-

Saturated Calomel Electrode

Construction: It consists of tube in which is a layer of mercury is placed at the bottom, over which a
paste of Hg+Hg2Cl2 is placed. The remaining portion of cell is filled with a solution of normal or
decinormal or saturated solution of KCl. A platinum wire dipping into the mercury layer is used for
making electrical contact. The side-tube is used for electrode is formulated as:

The calomel electrode can acts as anode or cathode depending on the nature of the other electrode
of the cell.
The net cell reversible electrode reactions,
Hg2Cl2(s) + 2 e– 2Hg (l) + 2 Cl–
2.303RT
E = E0 – log [Cl–]2
nF

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2.303RT
E = E0 – log [Cl–] , where n=2
F
E = E0 – 0.0591 log [Cl–] at 298K
Therefore electrode potential of calomel electrode is depending upon the concentration of KCl. The
electrode is reversible with chloride ions.
The electrode can be coupled with hydrogen electrode containing solution of unknown pH.
The potential of the calomel electrode depends upon the concentration of KCl solution used. Following
table gives the values of std. oxidation potentials for different concentrations of KCl solution used.
(measured at 298K).

Concentration of KCl Saturated KCl 1M KCl 0.1M KCl

E0 [v] 0.241 0.281 0.334
Applications:-
1. It is used as secondary reference electrode in the measurement of single electrode.
2. It is used as reference electrode in all potentiometer determinations and to measure pH of the given
solution.

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Lecture-13
Corrosion Engineering: Theories of Corrosion
Introduction:-
The process of destruction (or deterioration) and consequent loss of a solid metallic material, due to chemical
or electrochemical attack by its environment is called corrosion.
Ex rusting of iron, when exposed to the atmospheric conditions. During this, a layer of reddish scale and
powder of oxide (Fe3O4) is formed, and the iron becomes weak. Another common example is formation of
green film of basic carbonate [CuCO3 + Cu(OH)2] on the surface of copper, when exposed to moist-air
containing carbon dioxide.
Cause of Corrosion:-
Metals exist in the form of oxides, sulphides, sulphates and carbonates. These chemically combined states of
metal known as ore has low energy and is thus thermodynamically stable state for metal. The metals are
extracted from these ores after supplying a large amount of energy.
Metals in the uncombined condition have a higher energy and are in an unstable state. It is their natural
tendency to go back to the low energy state i.e., combined state by recombining with the elements present
in the environment. This is the main reason for corrosion.

Although corroded metal is thermodynamically more stable than pure metal but due to corrosion useful
properties of a metal such as malleability, ductility and electrical conductivity is lost.
Effects of corrosion:-
The effects of corrosion are the following;
1. Loss of useful properties of metal and thus loss of efficiency.
2. Replacement of corroded equipment.
3. High maintenance costs such as repainting.
4. Contamination of the product.
5. Due to failure, the plant shuts down.
6. Pollution due to a corrosion product affects the health.
Corrosion can be prevented by;
1. Proper design and use of suitable material.
2. Cathodic and anodic protection.
3. Treatment of metals.
4. External influences and
5. Environmental modifications.

Dry (or) Chemical Corrosion:-

This type of corrosion occurs mainly through the direct chemical action of environment/atmospheric gases
such as oxygen, halogen, hydrogen sulphide, sulphur dioxide, nitrogen or anhydrous inorganic liquid with
metal surfaces in immediate proximity. There are three main types of chemical corrosion.

1) Oxidation Corrosion: -
Oxidation corrosion is brought about by the direct action of oxygen at low or high temperatures on metals,
usually, in the absence of moisture. At ordinary temperatures, metals, in general, are slightly attacked. Alkali

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metals (Li, Na, K, Rb, etc.) and alkaline-earths (Be, Ca, Sr, etc.) are rapidly oxidized at low temperatures. At
high temperatures, almost all metals (except Ag, Au, and Pt) are oxidized.
The reactions in the oxidation corrosion are :

Mechanism:-
Oxidation occurs first at the surface of the metal and the resulting metal oxide scale forms a barrier that
tends to restrict further oxidation. For oxidation to continue either the metal must diffuse outwards through
the scale to the surface or the oxygen must diffuse inwards through the scale to the underlying metal. Both
transfers occur, but the outward diffusion of metal is, generally, much more rapid than the inward diffusion
of oxygen, since the metal ion is appreciably smaller than the oxygen iron and consequently, of much higher
mobility.
Nature of the oxide formed plays an important part in oxidation corrosion process.
Metal + Oxygen —
—→ Metal oxide (corrosion product)

When oxidation starts, a thin layer of oxide is formed on the metal surface and the nature of this film
decides the further action. Metal oxide layers are of the following types
(i) Stable metal oxide layer:- The corrosion forms stable oxide film which is impervious or tightly
adhering as seen in Cu or Al. This impervious coating will prevent further corrosion.
(ii) Unstable metal oxide layer:- Sometimes the oxide film decomposes back to metal and oxygen. In
such conditions the corrosion is not possible. This is seen mostly in Ag, Al, and Pt. i.e., the oxide layer formed
decomposes back into the metal and oxygen.
Metal oxide = Metal + Oxygen

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(iii) Volatile Metal Oxide Layer:- In some metal surfaces, the oxide film gets volatized as soon as it is
formed. This condition exposes the metal surface again and increases corrosion rapidly. Mostly seen in
molybdenum.

(iv) Porous metal oxide layer:- If metal oxide layer having pores or cracks. At certain times the oxygen
passes through pores or cracks of the layer to the underlying metal surface and continues corrosion till the
entire metal is converted to metal oxide. This type of metal oxide is observed in iron.

Pilling-Bed Worth Rule:-

Pilling-Bed worth rule describes the porous and non-porous nature of metallic oxide which is formed during
corrosion.
According to this rule the specific volume ratio is calculated as follows:
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑚𝑒𝑡𝑎𝑙 𝑜𝑥𝑖𝑑𝑒
𝑠𝑝𝑒𝑐𝑖𝑓𝑖𝑐 𝑣𝑜𝑙𝑢𝑚𝑒 𝑟𝑎𝑡𝑖𝑜 =
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑚𝑒𝑡𝑎𝑙
a) If the specific volume ratio is smaller, then oxidation corrosion will takes place because the oxide films will
be sufficiently porous for diffusion of 𝑀n+𝑎𝑛𝑑 𝑂2–.
b) If volume of the metal oxide ≥ volume of the parent metal, then it will be non-porous.
c) If the volume of the metal oxide < volume of the parent metal, then it will be porous

Corrosion by Other Gases: -

Corrosion by other gases like SO2, CO2, Cl2, H2S, F2, etc. The extent of corrosive effect depends mainly on the
chemical affinity between the metal and the gas involved. The degree of attack depends on the formation of
protective or non-protective films on the metal surface.
(a) If the film formed is protective or non-porous (e.g., AgCl film, resulting from the attack of Cl2 on Ag), the
intensity or extent of attack decreases, because the film formed protects the metal from further attack.
2Ag + Cl2 2AgCl
(b) If the film formed is non-protective or porous, the surface of the whole metal is gradually destroyed. For
example, dry Cl2 gas attacks on tin (Sn) forming volatile SnCl4 (which volatilizes immediately), thereby leaving
fresh metal surface for further attack. Similarly, in petroleum industry, H2S at high temperature attacks steel
forming a FeS scale, which is porous and interferes with normal operations.
Sn + 2Cl2 SnCl4

Liquid Metal Corrosion: -

Liquid metal corrosion is due to chemical action of flowing liquid metal at high temperatures on solid metal
or alloy. Such corrosion occurs in devices used for nuclear power. The corrosion reaction involves either: (i)
dissolution of a solid metal by a liquid metal or (ii) internal penetration of the liquid metal into the solid metal.
Both these modes of corrosion cause weakening of the solid metal.

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Lecture-14
Theories of Corrosion, Types of Corrosion
Wet (or) Electrochemical Corrosion:-
Electrochemical corrosion occurs: (i) when a conducting liquid is in contact with metal or (ii) when two
dissimilar metals or alloys are either immersed or dipped partially in a solution. This corrosion occurs, due to
the existence of separate ‘anodic’ and ‘cathodic’ areas/parts, between which current flows though the
conducting solution. At anodic area, oxidation reaction (i.e., liberation of free electrons) takes place, so
anodic metal is destroyed by either dissolving or assuming combined state such as oxide, etc. Hence,
corrosion always occurs at anodic areas.

On the other hand, at cathodic areas, reduction reaction (i.e., gain of electrons) takes place. Usually, cathode
reactions do not affect the cathode, since most metals cannot be further reduced. So at cathodic part,
dissolved constituents in the conducting medium accept the electrons to form some ions (like OH– , O2– ) .
The metallic ions (at anodic part) and non-metallic ions (formed at cathodic part) diffuse towards each other
through conducting medium and form a corrosion product somewhere between anode and cathode. The
electrons set free at the anode flow through the metal and are finally consumed in the cathodic reaction.
Thus, we may sum up that electrochemical corrosion involves:
(i) the formation of anodic and cathodic areas or parts in contact with each other,
(ii) presence of a conducting medium,
(iii) corrosion of anodic areas only, and
(iv) Formation of corrosion product somewhere between anodic and cathodic areas.
Mechanism:-
On the other hand, the cathodic reaction consumes electrons either by: (a) evolution of hydrogen or (b)
absorption of oxygen, depending on the nature of the corrosive environment.
(a) Evolution of Hydrogen:- This corrosion occurs, usually, in acidic environments. Considering metal like Fe,
the anodic reaction is dissolution of iron as ferrous ions with the liberation of electrons.

Fe → Fe 2+ + 2e – (Oxidation)

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These electrons flow through the metal, from anode to cathode, where H + ions (of acidic solution) are
eliminated as hydrogen gas.
2H+ + 2e– — —→ H 2 (Reduction)
The overall reaction is : Fe + 2H + — —→ Fe + + H 2
2

Thus, this type of corrosion causes “displacement of hydrogen ions from the acidic solution by metal ions”.
Consequently, all metals above hydrogen in the electrochemical series have a tendency to get dissolved in
acidic solution with simultaneous evolution of hydrogen.
(b) Absorption of Oxygen:- Rusting of iron in neutral aqueous solution of electrolytes (like NaCl solution) in
the presence of atmospheric oxygen is a common example of this type of corrosion. The surface of iron is,
usually, coated with thin film of iron oxide. However, if this iron oxide film develops some cracks, anodic
areas are created on the surface, while the well metal parts act as cathodes. It follows that the anodic areas
are small surface parts, while nearly the rest of the surface of the metal forms large cathodes.

At anodic areas of the metal (Fe) dissolve as ferrous ions with liberation of electrons.

The liberated electrons flow from anodic to cathodic areas through iron metal, where electrons are
intercepted by the dissolved oxygen as

The Fe+2 ions and OH- ions diffuse and then they meet, ferrous hydroxide is precipitated.

1. If enough oxygen is present, ferrous hydroxide is easily oxidized to ferric hydroxide.

This product is called Yellow rust actually corresponds to Fe2O3.H2O

2. If the supply of oxygen is limited, the corrosion product may be even black anhydrous magnetite, Fe3O4.

Types of Wet (or) Electrochemical Corrosion

1) Galvanic Corrosion:-
When two dissimilar metals (e.g, Zn and Cu) are electrically connected and exposed to an electrolyte, the
metal higher in electrochemical series undergoes corrosion. This type of corrosion is called galvanic
corrosion. In the above example, Zn (higher in electrochemical series) forms the anode and is attacked and
gets dissolved; whereas Cu (lower) acts as cathode.

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Mechanism:-
In acidic solution, the corrosion occurs by the hydrogen evolution process; while in neutral or slightly alkaline
solution, oxygen absorption occurs. The current flows from anode to cathode.

Thus, it is evident that the corrosion occurs at the anodic metal; while the cathodic part is protected.
Ex:-[Link] screws in a brass marine hardware.
[Link]-Sb solder around copper wire.

Pitting Corrosion:-
Pitting corrosion is a localized accelerated attack, resulting in the formation of cavities around which the
metal is relatively unattached. Thus, pitting corrosion results in the formation of pinholes, pits and cavities in
the metal. Due to the cracking of the protective film on a metal at specific points, small anodic and large
cathodic areas are formed. Breakdown of the protective film may be caused by : (i) surface roughness or non-
uniform finish, (ii) scratches or cut edges, (iii) local straining of metal, due to non-uniform stresses, (iv)
alternating stresses, (v) sliding under load, (vi) impingement attack (caused by turbulent flow of a solution
over a metal surface), and (vii) chemical attack.
Ex: stainless steel and aluminum show characteristic pitting in chloride solution.
The presence of the extraneous impurities (like sand, dust, scale, etc.) embedded on the surface of metals
also lead to pitting. Owing to the differential amount of oxygen in contact with the metal, the small part
(underneath the impurity) becomes the anodic areas and the surrounding large parts become the cathodic
areas. Intense corrosion, therefore, start just underneath the impurity. Once a small pit is formed, the rate
of corrosion will be increased.

Waterline corrosion:-
When water is stored in a steel tank, it is generally found that the maximum amount of corrosion takes place
along a line just beneath the level of the water meniscus .The area above the waterline (highly-oxygenated)
acts as the cathodic and is completely unaffected by corrosion. However, if the water is relatively free from
acidity, little corrosion takes place.

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The problem of waterline corrosion is also that concerns marine engineers. In the case of ships, this kind of
corrosion is often accelerated by marine plants attaching themselves to the sides of ships. The uses of special
antifouling paints restrict this to some extent.

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Lecture-15
Factors Affecting the Rate of corrosion

Factors influencing corrosion:-

The rate and extent of corrosion, depends on the following factors:
1. Nature of the metal:-
(i) Position in galvanic series: - When two metals or alloys are in electrical contact, in presence
of an electrolyte, the more active metal (or higher up in the series) suffers corrosion. The rate
and severity of corrosion, depends upon the difference in their positions, and greater is the
difference, the faster is the corrosion of the anodic metal/alloy.
(ii) Overvoltage: - Corrosion rate is inversely proportional to the over voltage of the metal in a
corrosive surroundings. e.g, the hydrogen over voltage of Zn in 1M H 2SO4 is 0.70v. So the rate
of corrosion is low. But when some Cu impurity is present, the over voltage is reduced and
corrosion rate increases.
(iii) Relative areas of the anodic and cathodic parts: - When two dissimilar metals or alloys are
in contact, the corrosion of the anodic part is directly proportional to the ratio of areas of the
cathodic part and the anodic part.
(iv) Physical state of metal:- The rate of corrosion is influenced by physical state of the metal
(such as grain size, orientation of crystals, stress, etc.). The smaller the grain-size of the metal
or alloy, the greater will be its solubility and hence, greater will be its corrosion. Moreover, areas
under stress, even in a pure metal, tend to be anodic and corrosion takes place at these areas.
(v)Nature of surface film:- In aerated atmosphere, practically all metals get covered with a thin
surface film (thickness= a few Angstroms) of metal oxide. The ratio of the volumes of the metal
oxide to the metal is known as a ‘specific volume ratio’. Greater the specific volume ratio, lesser
is the oxidation corrosion rate. The specific volume ratios of Ni, Cr, and W are 1.6, 2.0 and 3.6
respectively. Consequently, the rate of oxidation of tungsten is least, even at elevated
temperatures.
2. Nature of the corroding environment:-
(i) Temperature:- With increase of temperature of environment, the reaction as well as
diffusion rate increase, thereby corrosion rate is generally enhanced.
(ii) Humidity of air:-Humidity of air is the deciding factor in atmospheric corrosion. “Critical
humidity” is defined as the relative humidity above which the atmospheric corrosion rate of
metal increases sharply. The value of critical humidity depends on the physical characteristics
of the metal as well as nature of the corrosion products. The reason why corrosion of a metal
becomes faster in humid atmosphere is that gases (CO2, O2 etc) and vapours, present in
atmosphere furnish water to the electrolyte, essential for setting up an electrochemical
corrosion cell.
(iii) Presence of impurities in a atmosphere:- Atmosphere, in the vicinity of industrial areas,
contains corrosive gases like CO2, H2S, SO2, and fumes of HCl, H2SO4 etc. In presence of these
gases, the acidity of the liquid, adjacent to the metal surfaces, increases and its electrical
conductivity also increases. This consequently, results in an increase of corrosion current
flowing in the local electrochemical cells on the exposed metal surfaces.

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iv) Influence of PH:- Generally, acidic media (i.e. PH < 7) are more corrosive than alkaline and
neutral media. However, amphoteric metals (like Al, Zn, Pb, etc.) dissolve in an alkaline solution
as complex ions.
(v) Conductance of the corroding medium:- In corrosion of underground or submerged
structures, the conductance of the medium is of prime importance. Conductance of dry sandy-
soils is lower than those of clayey and mineralized soils. Consequently, stray currents (from
power leakages) will cause more severe damage to the metallic structures, buried under clayey
and mineralized soils than those under dry sandy-soils.
(vi) Formation of oxygen concentration cell: - With the increase in supply of oxygen/air to the
moist-metal surface, the corrosion is promoted. Less oxygen concentration (e.g. oxide-coated
part or less-exposed part) parts becomes anodic; while the more-oxygenated regions (or parts
more exposed to oxygen) becomes cathodic, thereby leading ot the formation of “oxygen-
concentration cell”in which the anodic part suffers corrosion.

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Lecture 16
Corrosion control methods
Cathodic protection:-
The principle involved in this method is to force the metal to be protected to behave like a
cathode, thereby corrosion does not occur. There are two types of cathodic protections:
(i) Sacrificial anodic protection method: - In this protection method, the metallic structure (to be
protected) is connected by a wire to a more anodic metal, so that all the corrosion is concentrated
at this more active metal. The more active metal itself gets corroded slowly; white the parent
structure (cathodic) is protected. The more active metal so-employed is called “sacrificial anode”.
The corroded sacrificial anode block is replaced by a fresh one, when consumed completely.
Metals commonly employed as sacrificial anodes are magnesium, zinc, aluminum and their alloys.
Important applications of sacrificial anodic method include protection of buried pipelines,
underground cables; marine structure, ship-hulls, water-tanks, piers, etc.

Sacrificial anodic protection Impressed current cathodic protection

(ii) Impressed current cathodic protection:- In this method, an impressed current is applied in
opposite direction to nullify the corrosion current, and convert the corroding metal from anode
to cathode. Usually, the impressed current is derived from a direct current source (like battery
or rectifier on a.c. line) with an insoluble anode (like graphite, high silica iron, scrap iron,
stainless steel or platinum). Usually, a sufficient D.C. current is applied to an insoluble anode,
buried in the soil (or immersed in the corroding medium), and connected to the metallic
structure to be protected .The anode is, usually, in a backfill (composed of coke breeze or
gypsum) so as to increase the electrical contact with the surrounding soil. This type of cathodic
protection has been applied to open water-box coolers, water-tanks, buried oil or water pipes,
condensers, transmission line towers, marine piers, laid-up ships, etc. This kind of protection
technique is, particularly, useful for large structures for long-term operations.

𝑁𝑖+2 + 2 𝑒– ——→ 𝑁𝑖
𝑁𝑖 +2 + 𝐻 𝑃𝑂– + 𝐻 𝑂 —
—→ 𝑁𝑖 + 𝐻 𝑃𝑂 –
+ 2𝐻+
2 2 2 2 3
In addition to these reactions, there may be formation of phosphorous which results in Ni-P alloy
deposition.
Applications:-
1. It is used in several component values, pistons, shafts and hydraulic systems.

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2. Electroless Ni-P coatings are used in electrical industry in making magnetic components.
3. Threading inside the tubings are nickel – plated.
4. Nickel electroless plating on acrylonitrile butadiene styrene polymer (ABS) is used in decorative items.

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Lecture-17
SURFACE COATINGS
Organic Coatings
Organic coatings are often liquid or powder paints that require several layers before a thick enough
coating is achieved to inhibit corrosion. The coating must be dense and durable.
These coatings are based on carbon containing materials normally derived from refined and/or modified
petroleum products, as well as different solvents/water, pigments, additives, and fillers.
Below are four organic coatings commonly used in industrial applications:
1. Polyurethane coatings – Enhanced with specialty additives, polyurethane coating products are
characterized by exceptional resistance to corrosion, abrasion, chemicals and weathering
processes. Due to this versatility, you will find polyurethane used as a primer, intermediate coat or
a topcoat depending on the needs of the application.
2. Epoxy coating systems – Epoxies define a large group of coating products, with excellent film-
building, mechanical and chemical properties. Epoxy coating systems can bond to different
surfaces. This makes them optimal choices for many industrial painting projects that demand
maximum protection against normal wear and tear, abrasion, corrosion, moisture, water, salt air,
fuels and chemicals, as well as non-oxidizing acids, alkali and salts in immersion. The most notable
limitation of the epoxy family of coatings is their poor performance in sunlight.

Paints
Paint is a mechanical dispersion mixture of one or more pigments in a vehicle. The ‘vehicle’ is a liquid,
consisting of non-volatile, film-forming material, drying oil and a highly volatile solvent, thinner. When
a paint is applied to a metal surface (usually by brushing or spraying), the thinner evaporates; while
the drying oil slowly oxidizes forming a dry pigmented-film.

Requisites of a good paint: A good paint possesses the following characteristics:

(1) It should be fluid enough to be spread easily over the protected surface.
(2) It should possess high covering power.
(3) It should form a quite tough, uniform, adherent and impervious film.
(4) Its film should not get cracked on draying.
(5) It should protect the painted surface from corrosion effects of environment.
(6) It should form film, the colour of which is quite stable to the effect of atmosphere and other agencies.
(7) Its film should be glossy (i.e., having shine or luster).
(8) Its film should be stable.
(9) It can be prepared in such a consistency as to be easily applicable with brush or spraying device and
that it yields a smooth and uniform surface.
(10) It should possess high adhesion capacity to the material ove which it is intended to be used.

CONSTITUENTS OF PAINTS:-
1. Pigment:-
Pigment is a solid substance, which is an essential constituent of paint. Its functions are to : (i) provide
capacity to paint, (ii) provide strength to paint, (iii) provide desired colour to paint, (iv) give aesthetical
appeal (i.e., pleasing to look at) to the paint film, (v) give protection to the paint film by reflecting harmful

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ultraviolet light, (vi) provide resistance to paint film against abrasion/wear. (vii) Improve the
impermeability of paint film to moisture, and (viii) increase wheather-resistance of the film.
Pigments used whites [such as white lead, zinc oxide, lithophone, titanium oxide] or coloured [(i) red-
red lead, ferric oxide, Venetian red, chrome red, (ii) green-chromium oxide, (iii) blue-prussian blue, (iv)
black-carbon black, Characteristics of good pigments : Good pigments should be : (i) opaque, (i)
chemically inert so that paint film has stability and longer life, (iii) non-toxic so that there is no bad effect
on the health of painter as well as inhabitants, (iv) freely mixable with film-forming constituent, oil, and
(v) cheap.
2. Vehicle or drying oil:-
Vehicle or drying oil is a film-forming constituent of the paint. These are glyceryl esters of high molecular-
weight fatty acids, generally, present in animal and vegetable oils.

The most widely used drying oil, are linseed oil, soya bean oil, and dehydrated castor oil.
Functions of drying oils:- Drying oil supplies to paint-film: (i) main film-forming constituent, (ii) vehicle
or medium, (iii) toughness, (iv) adhesion, (v) durability, and (vi) water-proofness.
Reactions in drying of oils:-
The oil film, after it has been applied on the protected surface, absorbs oxygen (of the air) at the double
bonds, forming peroxides, di peroxides and hydro peroxides, which isomerise, polymerize and condense
to form a characteristic tough, coherent, hard, elastic, insoluble, infusible, highly cross-linked structured
macromolecular film. The final hardened product actually resembles a thermosetting resin in chemical
structure.
3. Thinners:-
i. Reduce the viscosity of the paint ot suitable consistency, so that it can easily be handled and
applied;
ii. Dissolve vehicle and the additives in the vehicle;
iii. Suspend the pigments;
iv. Increase the penetration power of the vehicle;
v. Increase the elasticity of the paint film;
vi. Help the drying of the paint film, as they evaporate.
Common thinners used are turpentine, mineral spirits (from petroleum), benzene, di pentene, naphtha,
xylol, kerosene, methylated napththalene, etc.

4. Driers:-
Driers are oxygen-carrier catalysis. They accelerate the drying of the oil-film through oxidation
polymerization and condensation. Thus, their main function is to improve the drying quality of the oil-
film.
The most effective driers are resonates, linoleates, tungstates and naphthenates of Co, Mn, Pb and Zn
5. Extenders or fillers:-
Extenders or fillers are low refractive indices materials, generally, of white colour, added to : (i) reduced
the cost, (ii) increase durability of the paint, (iii) provide negligible covering power to the paint, (iv) help

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to reduce the cracking of dry paint film and sometimes help to keep the pigments in suspension, (iv)
serve to fill voids in the film, (vi) increase random arrangement of pigment of pigment particles, and (vii)
act as carrier for the pigment colour.
Important extenders used are barites (BaSO4), talc, asbestos, ground silica, gypsum, ground mica, state
powder, china-clay, whitting (CaCO3), magnesium silicate, diamite clay, calcium sulphate, etc.
6. Plasticizers:-
Sometimes, plasticizers are incorporated in the paint: (i) to provide elasticity to the film, and also (ii) to
minimize its cracking. Common plasticizers used are tri cresyl phosphate, tri phenyl phosphate, tri butyl
phthalate, di amyl phthalate and di butyl tartarate.
7. Antiskinning agents:-
Antiskinning agents are, sometimes, added to some paints with the object preventing gelling and
skinning of the paint film. Important antiskinning agents are polyhydroxy phenols.

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Lecture-18
Surface Coatings
Methods of application of metal coatings:-
(1) Hot dipping:-
Hot dipping is used for producing a coating of low-metal such as Zn (m.p. = 4190C), Sn (m.p.=2320C),
Pb, Al, etc. on iron, steel and copper, which have relatively higher melting points. The process, in general,
consists of immersing the base metal in a bath of the molten coating-metal, covered by a molten flux
layer (usually zinc chloride). The flux cleans the base metal surface and prevents the oxidation of the
molten coating-metal. For good adhesion, the base metal surface must be very clean; otherwise it
cannot be properly wetted by the molten metal. Two most widely applied hot dipping methods are:
(a) Galvanizing:-
Galvanizing is the process of coating iron or steel sheets with a thin coat of zinc to prevent them from
rusting. The process is carried out as follows: The iron or steel article (e.g., sheet, pipe, and wire) is first
cleaned by pickling with dilute H2SO4 solution for 15-20 minutes at 60-900C. This treatment also removes
any scale, rust (oxide layer) and impurities. The article is then washed well and dried. It is then dipped
in bath of molten zinc, maintained at 425-4300C. The surface of the bath is kept covered with a flux
[NH4Cl] to prevent oxide formation. When the article is taken out, it is found to have been coated with
a thin layer of zinc. It is then passed through a pair of hot rollers. This process removes any superfluous
(excess) of zinc and produces a thin film of uniform thickness. Then, it is annealed at a temperature of
6500C and finally, cooled slowly.

Uses:- It is most widely used for protection of iron from atmospheric corrosion in the form of roofing
sheets, wires, pipes, nails, bolts, screws, buckets, tubes, etc. It may be pointed here that zinc gets
dissolved in dilute acids to form highly toxic (or poisonous) compounds. Hence, galvanized utensils
cannot be used for preparing and storing foodstuffs, especially acidic ones.

(b) Tinning: -
Tinning is coating tin over the iron or steel articles. The process consists in first treating steel sheet in
dilute sulphuric acid (pickling) to remove any oxide film. After this, it is passed through a bath of zinc
chloride flux. The flux helps the molten metal to adhere to the metal sheet. Next, the sheet passes
through a tank of molten tin and finally through a series of rollers from underneath the surface of a layer
palm oil .The palm oil protects the hot tin-coated surface against oxidation. The rollers remove any
excess of tin and produce a thin film of uniform thickness on the steel sheet.

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Uses: -
Tin possesses considerable resistance against atmospheric corrosion. Moreover, because of non-
toxic nature of tin, tinning is widely used for coating steel, copper and brass sheets, used for manufacturing
containers for storing foodstuffs, ghee, oils, kerosene and packing food materials. Tinned-copper sheets are
employed for making cooking utensils and refrigeration equipments.

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