UNIT-III

ELECTRO CHEMISTRY AND CORROSSION

ELECTRO CHEMISTRY

Introduction:
 Electrochemistry is the branch of chemistry which deals with the transformation of
electrical energy into chemical energy and vice versa or the study of the interchange
between chemical change and electrical work.
 Systems utilizing a redox reaction to produce or use electrical energy.
 Electrochemistry deals with the relationship between electrical, chemical phenomena and
the laws of interaction of these phenomena. The branch of electrochemistry is of major
technical importance.
 The laws of electrochemistry form the basis of electrolysis and electro synthesis. The
knowledge of electrochemistry is of immense importance to study about the causes of
destruction of materials due to corrosion. In electro-chemistry, there are two processes, both
these processes are interrelated.
Cell:
Cell is a device or apparatus which is going to convert electrical energy to chemical energy or
chemical energy to electrical energy.
 The two processes above can be summarized as follows:
1. Electrolytic cell: Electrical energy is converted in to chemical energy in electrolytic cell.
Ex: Electrolysis process.
2. Electrochemical cell: Chemical energy is converted in to electrical energy in
Electrochemical cell.
Ex: Galvanic cell or voltaic cell (Daniel cell).
Electrode:
An electrode is electrical conductor used to make contact with a nonmetallic part of a circuit.
Electrode potential:
The tendency of metallic electrode to lose or gain electrons, when it is in contact with its own
solution (salt) is called “Electrode Potential”.
a) Oxidation Potential: The tendency of metallic electrode to lose of electrons is called
“Oxidation Potential”.
b) Reduction Potential: The tendency of metallic electrode to gain of electrons is called
“Reduction Potential”.
It is quite obvious that the value of reduction potential negative of its oxidation potential and
vice versa. Thus, the oxidation potential of an electrode is + x volt, then its reduction
potential will have a value of – x volt.
Single Electrode Potential (E):
It is the measure of tendency of a metallic electrode to lose or gain electrons, when it is in
contact with a solution of its own salt.
Measurement of Single Electrode potential:

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Single electrode potential cannot be directly measured. The single electrode potential of a
half-cell depends on
1. Concentration of the ions in the solution
2. Tendency to form ions
3. Temperature
The single electrode potential is conveniently measured by combining the half-cell with a
standard electrode or reference electrode and measuring the total EMF of a cell
E (cell) = E (right) – E (left)
If the standard cell acts as Anode the equation becomes

E (cell) = E (right) – E0
If the standard cell acts as Cathode the equation becomes

E (cell) = E0 – E (left)
0
Where E = Standard electrode potential
Standard Electrode Potential (E°):
It is the measure of tendency of a metallic electrode to lose or gain electrons, when it is in
contact with a solution of its own salt of 1M (Molar) concentration at 25 °C.
(Or)

The potential exhibited by a single electrode at unit concentration of the concerned metal ion
or non-metal ion solution at 25°C is called standard electrode potential.
Types of Electrodes:
 It is impossible to measure or determine the absolute value of a single electrode potential.
But we can measure the potential difference between two electrodes potentiometrically by
combining them to form a complete cell.
 For this purpose “reference electrode” is used. Standard Hydrogen Electrode (SHE) is the
commonly used reference electrode, whose potential has been arbitrarily fixed as zero.
 The EMF of the cell is measured and it is equal to the potential of electrodes.

Reference electrode (or) Standard electrodes:

 The electrode potential is found out by coupling the electrode with another reference
electrode, the potential of which is known or arbitrarily fixed as zero.
 The important primary reference electrode used is a standard hydrogen electrode, standard
electrode potential of which is taken as zero. But it is very difficult to set up a standard
hydrogen electrode because:
i) It is very difficult to maintain the concentration of H+ ions at 1M and pressure of H2 gas at
1atm.
ii) Hydrogen electrode gets poisoned if there is traces of impurities in the solution or gas.
To overcome this problem other electrodes are needed, other electrodes are called
“Secondary reference Electrodes”.
Secondary reference electrodes are 3 types.
a) Calomel electrode
b) Glass electrode (Internal reference electrode)

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c) Quinhydrone electrode

Calomel electrode:
Calomel electrode is particularly very simple to construct, free from surface sensitivity and
accurate to use even in a very normal laboratory. The calomel electrode consists of an inner
glass tube and an outer jacket. In the inner glass tube a platinum wire is dipped into mercury
which rests on a paste of mercurous chloride, Hg2Cl2 (commercially known as calomel) and
mercury. This paste is in contact with KCl present in the outer jacket, through the glass frit
plug fixed at the bottom of inner glass tube. The calomel electrode comes in contact with the
experimental solution through a frit arranged to the outer jacket. The potential of this
electrode depends on the concentration of KCl taken in the outer jacket. Some of the most
popularly used concentrations of KCl and corresponding single electrode (reduction)
potentials on the hydrogen scale at 25°C are given below;
1. 0.1M KCl | Hg2Cl2 (s) | Hg, E0 =0.3338 V
2. 1.0M KCl | Hg2Cl2 (s) | Hg, E0= 0.2800 V
3. Saturated KCl | Hg2Cl2 (s) | Hg, E0= 0.2422V

When the calomel electrode acts as Anode

When the calomel electrode acts as Cathode

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 Calomel electrode is represented as

Hg, Hg2Cl2 (S), KCl (Sat. Solution); E° = 0.2422 V
 Hg2Cl2 get reduced to form Hg22+ ions.
 Here the concentration of Cl- ion gets increased.
 The electrode potential of calomel electrode is:

ECalomel = E°Calomel - log [ ]

The electrode potential depends on the activity of the chloride (Cl-) ions and the activity of
the Cl- ions increases than electrode potential decreases.

Glass electrode (or)Internal reference electrode:

 A glass electrode consists of thin-walled glass bulb. The glass is a special type having low
melting point and high electrical conductivity. A glass electrode containing a Pt wire in
0.1M HCl solution. The glass electrode is represented as:

Pt, 0.01M HCl / Glass

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 HCl in the bulb furnishes a constant H+ ion concentration. Glass electrode is used as the
“internal reference electrode”. By using a glass electrode, the pH of the solutions can be
determined. The thin walled glass bulb called glass membrane functions.
 The EMF is given below:

E G = E °G - log [H+] (from Nernst equation)

E G = E °G - log [H+]

EG = E°G - 0.0591 log [H+]

EG = E°G + 0.0591 pH

From the equation it is clear that the pH of solution is a direct measure of EMF of a glass
electrode.

Determination of pH of a solution using Glass electrode:

The glass electrode is placed in the solution under test and it is coupled with saturated
calomel electrode as shown in figure. The cell filled with solution of unknown pH and this
solution is coupled with calomel electrode by using salt bridge. The glass electrode inserted
in the solution of unknown pH. The two electrodes i.e. glass electrode and calomel electrode
are connected together then EMF of the cell is measured.

From the EMF, the pH of the solution is calculated as follows:

Ecell = E right – E left

Ecell = E cal – E G
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Ecell = E cal – (E°G + 0.0591 pH)

Ecell = E cal – E°G - 0.0591 pH)

pH =

Advantages of glass electrode:

1) It can be easily constructed and readily used.
2) The results are accurate.
3) It is not easily poisoned.

Disadvantages of glass electrode:

The glass electrode can be used in solutions only with pH range of 0 to 10. However above
the pH = 12 (high alkalinity) cations of the solution affect the glass and make the electrode
useless.

Quinhydrone electrode:
Quinhydrone is a 1:1 molar mixture of quinine and hydroquinone. It is a type of redox
electrode which can be used to measure the H+ ion concentration of a solution. The electrode
consists of an inert metal electrode (a platinum wire) in contact with Quinhydrone crystals
and a water-based solution. Quinhydrone is slightly soluble in water, formed by equimolar
mixture of hydroquinone and Quinone.

Each one of the two substances can be easily oxidised or reduced to other. In this case the
electrode reaction represented as follows

Using Nernst equation the potential of Quinhydrone electrode (EQ) written as

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- [ ][ ]
EQ = log

= standard potential of the quinhydrone electrode

Since [Q] = [QH2], concentration of quinone and hydroquinone are equal.

EQ = – 0.0591 log [H+] at 25°C

EQ = + 0.0591 pH

pH =
Determination of pH of a solution using Quinhydrone electrode:

Add a pinch of Quinhydrone powder to the experimental solution, then Pt electrode is

inserted in it. For determining pH value, this half-cell is combined with other reference
electrode (Calomel) and the EMF of the cell is determined potentiometrically.
The cell represented as

Ecell = E calomel – E Quinhydrone

= 0.2422 V – ( + 0.0591pH)

0.6994 – 0.2415 + Ecell = 0.05916 pH

pH =

Advantages & limitations of Quinhydrone electrode:

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1. The electrode is very easy to set up and the pH value obtained is very accurate.
2. Very small quantities of the solution are sufficient for the measurement.
3. The electrode cannot be useful in more alkaline (pH>8.5) solutions and the solution
which react with Quinhydrone or Quinone.

Galvanic series (or) Electrochemical series:

When the various electrodes (metals) are arranged in the order of their increasing values of
standard reduction potential on the hydrogen scale then the arrangement is called as electro
chemical series.
(Or)
When the various electrodes (metals) are arranged in the order of their decreasing values of
standard oxidation potential on the hydrogen scale then the arrangement is called as electro
chemical series.

The standard electrode potential of a number of electrodes are given in table. This values are
determined potentiometrically by combining the electrode with another standard electrodes
whose electrode potential is zero.

Electrode Electrode reaction E° volts Nature

Li+ / Li -3.05 Anodic (Base)

Mg+2 / Mg -2.37

Zn+2 / Zn -0.76

Fe+2 / Fe -0.44

Sn+2 / Sn -0.14

Pb+2 / Pb -0.13

H+ / H2 0.00 Reference - Pt

Cu+2 / Cu +0.34

Ag+ / Ag +0.80

Au+ / Au +1.69

F2 / +2.87 Cathodic (Noble)

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i) The higher the metal in the series, the greater is its tendency to be oxidized.
ii) The metals high up in the series are strong reducing agents and their ions are stable
whereas those near the bottom of the series are inactive stable metals and their ions are
easily reduced to metals. Any metal can reduce any cation below it in the series of one
molar solutions are used.
iii) Any metal above hydrogen will displace hydrogen (H) from dilute acid solution.

Ex:

Because the metal with positive reduction potential (i.e. the metals placed below H2 in the
EMF series) will not displace the hydrogen from an acid solution.
iv) The oxidized form of any metal below the hydrogen in the series will be reduced by
hydrogen.
v) The metals above the hydrogen in the series can easily displace the metal below the
hydrogen in the series from its salt solution.

Ex:

Applications of electrochemical series:

1. It gives information about the relative ease with which oxidation and reduction of
metals occur.
2. Information about the replacement tendencies of metals.
3. Information about the relative corrosion tendencies of metals and alloys.
4. Predicts spontaneity of redox reactions.

Nernst equation:
As given in the electrochemical series, an electrode or half Cell is said to have a standard
value of reduction potential if the concentration of electrolyte is 1M at 298K. Nernst found
that the single electrode potential (Reduction potential) varies with the change in
concentration of ions and temperature and hence the EMF of the cell also varies. Walter
Nernst (1889) derived a mathematical relationship between the standard electrode potential,
temperature and the concentration of ions. This relationship is known as the Nernst equation.

Consider the following redox reaction

For such a redox reversible reaction, the free energy change (∆G) and its equilibrium constant
(k) are interrelated as

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[ ]
∆G = - RT lnk + RT ln
[ ]
[ ]
∆G = ∆G° + RT ln ---------- 1 (∆G° = - RT lnk)
[ ]
Equation 1 is Vanthoff‟s isotherm. Where ∆G° = standard free energy change.

The decrease in frequency (- ∆G) in the above reaction will produce electrical energy.

In the cell, if the reaction involves transfer „n‟ number of electrons, then the „n‟ faraday of
electricity will flow.

If „E‟ is the EMF of the cell, then the total energy (electricity) produced in the cell is

nFE = - ∆G° (∆G° = - nFE°, ∆G = -nFE) --------------- 2

Comparing equation 1 &2

[ ]
– nFE = - nFE° + RT ln --------------------------- 3
[ ]

Dividing the above equation 3 by –nF and the activity of solid metal [M] = 1

E = E° - ln
[ ]

E = E° + ln [ ]

E= + log [M+n] -------------- 4

Where E = Single Electrode potential of the metal
E0 = Standard EMF of the cell for 1M solution at 298K.
R = Gas constant (8.314 JK-1 mol-1)
T = Kelvin temperature or absolute temperature (298K (or) 250c)
n = Number of electrons involved in the cell reaction or valency of ions
F = Faraday of electricity, i.e., 96,500 coulombs.
In equation 4 all the values are substituted

E= + log [M+n]

E= + log [M+n] ----------------- 5

Similarly, Nernst equation for oxidation potential follows as:

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E= - log [M+n] --------------- 6

The above equation 5 & 6 are known as Nernst equation for single electrode potential.

Applications of Nernst Equation:

1. It can be used to study the effect of electrolyte concentration on electrode potential.
2. It can be used for the calculation of the electrode potential of a cell.
3. Corrosion tendency of a metal can be predicted.
4. Determination of unknown concentration of one of the ionic species in a cell is possible
with the help of Nernst equation, provided Ecell and concentration of other ionic species are
known.
5. The pH of a solution can be calculated from the measurement of EMF and Nernst
equation.
6. It can be also be used for finding the valency of an ion or the number of electrons involved
in the electrode reaction.

Numerical Problems:
1. What is the potential of a lead electrode that is in contact with a solution of 0.015 M
Pb2+ ions. Standard electrode potential (E°) for is 0.13volts.

Solution:
Standard oxidation potential is given as

Concentration of (Pb2+) = 0.015 M

The Nernst equation for oxidation potential of Pb is

E = E° - log [Pb2+]

E = E° - log [Pb2+]

= 0.13 - log [0.015]

= 0.13 – 0.02955 (- 1.824)

= 0.13 + 0.0539
= 0.184 volts.
Oxidation potential of Pb = 0.184 V.

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2. Calculate the electrode potential of zinc electrode dipped in 0.1 M ZnSO4 solution at
25° C.
Solution:

Concentration of ZnSO4 = 0.1 M; n=2

E° Zn2+/Zn = -0.763 V (Known Standard reduction potential); E=?
The Nernst equation for reduction potential of Zn2+ is

E = E° + log [Zn2+] at 25° C

E = E° + log [Zn2+]

= - 0.763 + log [0.1]

= - 0.763 + (- 0.02955)
= - 0.79255 V.
Reduction potential of Zn = - 0.79255 V.
3. Calculate the standard electrode potential of zinc electrode dipped in 0.1 M ZnSO4
solution at 25° C. (E° Zn/Zn2+ = 0.76V)
Solution:
Concentration of ZnSO4 = 0.1 M; n=2
E° Zn/Zn2+ = 0.76 V (Oxidation potential); E=?
The Nernst equation for oxidation potential of Zn2+ is
E = E° - log [Zn2+] at 25° C

E = E° - log [Zn2+]

= 0.76 - log [0.1]

= 0.76 - 0.02955 (-1)

= 0.76+0.02955
= 0.7896 V
Reduction p of Zn = 0.7896 V.
4. Calculate the reduction potential of Cu2+/Cu = 0.5 M ZnSO4 at 25° C. (E° Cu2+ /Cu=
0.337V)
Solution:
Concentration of [Cu2+] = 0.5 M; n=2
E° Cu2+/Cu = 0.337 V; E=?
The Nernst equation for reduction potential of Cu2+ is
E = E° + log [Cu2+]

E = E° + log [Cu2+]

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= 0.337 + log [0.5]

= 0.337+ 0.02955 (-0.3010)

= 0.337 - 0.0089
= 0.328 V
Reduction potential of Cu = 0.328 V.
5. The EMF of Weston Cadmium cell is 0.683 volt at 25° C. if the reduction potential of
mercury electrode is 0.283, what would be the oxidation potential at the cadmium
electrode?
Solution:
The Weston Cadmium cell is represented as

E° (cell) = E° (right) – E° (left)

E° (cell) = E°Hg2+/Hg – E° Cd2+/Cd
E°=0.683V; E°Calomel (right) =0.283V
E° Cd2+/Cd (left) =?
0.683=0.283- E° Cd2+/Cd
E° Cd2+/Cd = 0.283-0.683 = -0.4 volts.
Reduction potential of Cd electrode = -0.4 V
Oxidation potential of Cd electrode = +0.4 V

Batteries:
Battery is a device which transforms chemical energy into electrical energy. The term battery
is usually applied to a group of two or more electrical cells connected together electrically in
series.

Characteristics:
 It should be light in weight and compact in size.
 The voltage of battery should not change much during its use.
 It should provide power for a longer period.

Types of Batteries: In general there are two types of batteries:

1. Primary batteries (or) Primary cells.

2. Secondary storage (or) Accumulator batteries (or) Secondary cells.

Primary batteries or Primary Cell:

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A primary cell is a battery that is designed to be used once and discarded, and not recharged
with electricity. In general, the electrochemical reaction occurring in the cell is not
reversible. Once the reactants have been converted to products, no electricity produced and
the cell becomes dead.

Examples of primary cells: Voltaic cells, Leclanche cell and lithium primary cell.

Lithium cells
Lithium cells belongs primary cells. The cells having lithium anodes are called lithium cells
irrespective of the cathode used. Lithium cells are classified into two types.
i) Solid cathode lithium cells.
ii) Liquid cathode lithium cells.

Solid cathode lithium cells (LiMnO2 cell):

 These systems may have solid or liquid electrolyte.
 The cathode MnO2 should be heated to > 300 °C to remove water before incorporating it in
the cathode.
 The electrolyte a mixture of propylene carbonate and 1, 2- dimethoxyethane.

Cell Reactions:
At Anode:

At Cathode:

Net cell reaction:

 Lithium being a light-weight metal, only 7 g (1 mole) material is required to produce 1 mole
of electrons.
 Li has the most negative E° value and therefore generates a higher voltage than the other
types of cells.
 Its cell voltage is high i.e. 3V.

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Liquid cathode lithium cells:

Liquid cathode lithium cells consists of a high-surface area carbon cathode, a non-woven
glass separator.
Lithium acts as anode, Thionyl chloride acts as electrolyte solvent and the active cathode.
The reactions of the cell can be represented as follows:

Cell Reactions:
At Anode:

At Cathode:

Net cell reaction:

The discharging cell voltage is 3.3 – 3.5 Volts.

Applications:
i) The cylindrical cells are used in fully automatic cameras.
ii) These cells are widely used in electronic devices such as calculators and watches.
iii) These cells are also used for military and space applications.
iv) These cells are also used in medical devices such as neuro stimulators, drug delivery
systems and also useful for electronic circuit boards for supplying fixed voltage.

Secondary storage or accumulator batteries:

The cell in which the cell reaction is reversed by passing direct current in opposite direction.
The secondary batteries can be used through a large number of cycles of discharging and
charging.
Examples
i) Lead-acid storage battery
ii) Nickel–cadmium battery
iii) Lithium-ion cell battery

Lead-acid cells:
If a number of cells are connected in series, the arrangement is called a battery. The lead
storage battery is one of the most common batteries that are used in the automobiles. A 12 V
lead storage battery is generally used, which consists of six cells, each providing 2 V. Each
cell consists of a lead anode and a grid of lead packed with lead oxide as the cathode. These
electrodes are arranged alternately, separated by a thin wooden piece and suspended in dil.
H2SO4 (5M or 38%), which acts as an electrolyte. Hence, it is called lead-acid battery.

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The cell may be represented as:

Anode: Sponge metallic Lead (Pb)

Cathode: Lead-dioxide (PbO2)
Electrolyte: 5M H2SO4
EMF: 2V
The half-cell reactions are:

At anode:

At cathode:

The overall reaction is

During discharging of battery, H2SO4 is consumed for the oxidation of Pb, hence the density
of H2SO4 falls, the battery needs recharging. In recharging, the cell operates like an
electrolytic cell i.e. electrical energy is supplied to it from an external source. The electrode
reactions are the reverse of those that occur during discharge.

The overall reaction is

During this process, lead and PbO2 is deposited at the respective electrodes and H2SO4 is
regenerated.
Applications:
Automobiles and construction equipment, standby/backup systems. Used mainly for engine
batteries, these cells represent over half of all battery sales. Some advantages are their low
cost, long life cycle, and ability to withstand mistreatment. They also perform well in high
and low temperatures and in high-drain applications.
Advantages:
 These cells have a low cycle life, a quick self-discharge, and low energy densities.
However, with a nominal voltage of 2V and power densities of up 600 W/kg, the lead-acid
cell is an adequate, if not perfect, design for car batteries.
 Rechargeable, portable constant potential at low cost.

Disadvantages:
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 Use of H2SO4 is dangerous its usage is fragile.

Lithium-ion batteries (or) Lithium-ion cells:

Lithium-ion battery is a secondary battery. As in lithium cell, it does not contain metallic
lithium as anode. As the name suggests, the movement of lithium ions are responsible for
charging & discharging. Lithium-ion cell has the following three components.
1. A positive electrode (Layers of lithium-metal oxide) (cathode).
2. A negative electrode (Layers of porous carbon) (anode).
3. An electrolyte (Polymer gel) (separator)
Construction:
The positive electrode is typically made from a layers of chemical compound called lithium-
cobalt oxide (LiCoO2).
The negative electrode is made from layers of porous carbon (C) (graphite).
Both the electrodes are dipped in a polymer gel electrolyte (organic solvent) and separated by
a separator, which is a perforated plastic and allows the Li+ ions to pass through.

Working of Lithium ion battery:

Charging Reaction:
During charging, Li+ ions flow from the positive electrode (LiCoO2) to the negative electrode
(graphite) through the electrolyte. Electrons also flow from the positive electrode to the
negative electrode. The electrons and Li+ ions combine at the negative electrode and deposit
there as Li.
LiCoO2 + C→ Li1-xCoO2 + CLix
Discharging Reaction:
During discharging, the Li+ ions flow back through the electrolyte form negative electrode to
the positive electrode. Electrons flow from the negative electrode to the positive electrode.
The Li+ ions and electrons combine at the positive electrode and deposit there as Li.
Li1-xCoO2 + CLix → LiCoO2 + C

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Advantages (or) Characteristics:
1. Lithium-ion batteries are high voltage and light weight batteries.
2. It is smaller in size.
3. It produces three time the voltage of Ni-Cd batteries.
4. It has none of the memory effect seen in Ni-Cd batteries.
Uses:
It is used in cell phone, note PC, portable LCD TV, semiconductor driven audio, etc.

CORROSSION
Definition: The surfaces of almost all metals begin to decay more or less rapidly, when
exposed to gaseous atmosphere, water or another reactive liquid medium. As a result of the
decay, the metals are converted to their oxides, hydroxides, carbonates, sulphides etc. The
process of decay or destruction or deterioration or decomposition of metal by
environmental attack is called corrosion.

Ex: formation of reddish brown scale and powder of rust on the surface of iron and formation
of blue green film of basic carbonate [CaCO3+ Cu(OH)2] on the surface of copper.
Cause of corrosion: Most metals (with the exception of noble metals such as Au, Pt, etc.)
exist in nature in combined forms as their oxides, carbonates, hydroxyl carbonates, sulphides,
chlorides and silicates. These are reduced to their metallic states from their ores, during their
extraction processes. During extraction of metals, considerable amounts of energy are
required. Consequently, isolated pure metals can be regarded in excited state (a higher energy
state) than their corresponding ores, and they have a natural tendency to revert back to
combined state (thermodynamically more stable state).

As a result when metals are put into use, in various forms, they are exposed to environment
such as dry gases, moisture, liquids, etc. the exposed metal surfaces begin to decay and forms
more stable compounds of metals like oxides, carbonates, etc. Thus, corrosion is a process
“reverse of extraction of metals”.

Effects of corrosion:
 The valuable metallic properties like conductivity, malleability, ductility etc. are lost due to
corrosion.
 The process of corrosion is very harmful and is responsible for the enormous wastage of
metallic products.

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 Losses occurring due to corrosion cannot be measured in terms of the cost of metals alone,
but the high cost of fabrication into equipment/machine tool/ structures should also be
considered.
 The approximate estimate of loss of metal due to corrosion, as 2 to 2.5 billion dollars per
annum all-over the world. Hence an engineer must understand the mechanism of corrosion
so that the effects can be minimized by avoiding the corrosion conditions and provide
simultaneous protection against corrosion.

Types of corrosion (Theories of corrosion):

The corrosion process proceeds in two types by chemical and electrochemical attack of
environment.
1) Dry corrosion / Chemical corrosion
2) Wet corrosion / Electrochemical corrosion

1) Chemical corrosion ( Dry corrosion ):

This type of corrosion occurs mainly through the direct chemical action of environment
/atmospheric gases such as oxygen, halogen, hydrogen sulphides, Sulphur dioxide, nitrogen
or anhydrous inorganic liquid with metal surfaces in immediate proximity.
There are three main types of chemical corrosion:
a. Oxidation corrosion
b. Corrosion by other gases
c. Liquid metal corrosion

a) Oxidation corrosion:
Direct action of oxygen at high or low temperatures on metals in the absence of moisture is
called oxidation corrosion. Generally metals oxidized to a smaller extent, however alkali
metals (Li, Na, K, Rb etc.) and alkaline earth metals (Be, Ca, Sr etc.) are even rapidly
oxidized at low temperatures. At high temperatures, almost all metals except Ag, Au and Pt
are oxidized.

Mechanism: The oxidation of the metal occurs at the surface first, resulting the formation of
metal oxide scale, which restricts further oxidation.
Further 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. Of the
two types of diffusions, the diffusion of the metal is rapid because the size of the metal ion is
smaller than oxygen ion, hence higher mobility to metal ion.

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Nature of the oxide formed plays an important part in oxidation corrosion process. The
following types of films are there:
Nature of the oxide formed plays an important role in oxidation corrosion process.
i) Stable metal oxide: A stable metal oxide layer with fine-grained structure tightly attached
to the parent metal surface. Hence, such a layer can be of impermeable nature to the attacking
oxygen. Such film behaves as a protective coating in nature, thereby protecting the metal
from further corrosion.
Ex. The oxide film on Al, Sn, Pb, Cu, Cr, W etc.

ii) Unstable metal oxide: the oxide layer formed decomposes back into the metal and
oxygen. Consequently, oxidation corrosion is not possible in such a case. Thus, Ag, Au, and
Pt do not undergo oxidation corrosion.

iii) Volatile metal oxide: the oxide layer formed evaporates as soon as it is formed, leaving
the underlying metal surface exposed for further attack. This causes rapid and continuous
corrosion, leading to excessive corrosion. Ex: Molybdenum oxide (MoO3) is volatile.

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iv) Porous metal oxide: Metal oxide layer having pores or cracks provides access to the
oxygen to reach the underlying surface of metal. As a result corrosion process continues
unobstructed, till the entire metal is completely converted into its oxide.

To express the extent of protection given by the corrosion layer to the underlying metal
Pilling Bedworth rule was postulated.

Pilling - Bedworth rule: “The ratio of the volume of the metal oxide formed to the
volume of the metal consumed is called Pilling – Bedworth ratio or specific volume ratio”.

Specific volume ratio = volume of metal oxide / volume of metal

Smaller the Specific volume ratio greater is the oxidation.

For example, the specific volume ratios of W, Cr and Ni are 3.6, 2.0 and 1.6 respectively.
Hence, the rate of corrosion is least in Tungsten (W).

If the volume of metal oxide is less than the volume of the metal, the oxide layer is porous,
non continuous and non-protective and faces strains. Hence cracks and pores are developed in
the layer, creating access to atmospheric oxygen to reach the underlying metal. In this case
corrosion is continuous and rapidly increases.
For example: Li, Na and K.

b) Corrosion by other gases:

The gases like SO2, CO2, Cl2, H2S and F2 etc. also causes chemical corrosion and the extent of
corrosion 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.

If the film formed is protective or non-porous, the intensity or extent of attack decreases,
because the film formed protects the metal from further attack.
Ex: AgCl film is protective and thus protect the metal from further attack of Cl2 on Ag.

If the film formed is non-protective or porous, the surface of the whole metal is gradually
destroyed.

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Ex: SnCl4 film is volatile and hence Sn under goes excessive corrosion

c) Liquid metal corrosion:

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 dissolution of a solid metal by a liquid metal or internal penetration of the liquid metal
into the solid metal. Both these modes of corrosion cause weakening of the solid metal.
Ex: Sodium metal leads to corrosion of Cadmium in nuclear reactor.

2) Electrochemical corrosion (Wet corrosion):

Wet corrosion or electrochemical corrosion takes place under wet or moist conditions through
the formation of short circuited electrochemical cells. Wet corrosion is more common than
dry corrosion. Electrochemical corrosion involves
1. Flow of electron-current between the anodic and cathodic areas.
2. The anodic reaction involves in dissolution of metal as corresponding metallic ions with
the liberation of free electrons.

At anodic area:

3. The electrons liberated at anode are transported to cathodic area through the metal.
4. On the other hand, the cathodic reaction either H+, O2, H2O consumes the electrons
generating non-metallic ions like OH- or O2- either by evolution of hydrogen or
absorption of oxygen, depending on the nature of corrosive environment.
Wet corrosion takes place by the following ways.

a) Evolution of hydrogen:

This type of corrosion occurs usually in acidic environments. The Rusting of iron takes place
in acidic medium
Considering metal like Fe the anodic reaction is dissolution of iron as ferrous ions with the
liberation of electrons.

+
These electrons flow through the metal, from anode to cathode, where H ions are eliminated
as hydrogen gas.

The net overall reaction is:

In Hydrogen Evolution type of corrosion the anodes are usually large and the cathodes are
small areas

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In Neutral medium at the cathode formation of OH- takes place along with the liberation of
hydrogen gas

The Fe2+ and OH- diffuse towards each other through the conducting medium forming the
corrosion product rust in between the cathodic and anodic areas.

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 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. If a crack is developed in this iron oxide film, the anodic areas
are created on the surface and well metal coated film parts act as cathode. It follows that the
anodic areas are small surface parts, while nearly the rest of the surface of the metal forms
large cathodes.
At the anodic area the metal (iron) oxidizes 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:

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2+ -
The Fe ion at anode and OH ions at cathode diffuse and when they meet ferrous hydroxide
is precipitated.

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

This product is called yellow rust, actually corresponds to 2 Fe2O3.3H2O.

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

Differences of chemical corrosion with electrochemical corrosion:

Chemical (or) Dry corrosion Electrochemical (or) Wet corrosion
This corrosion occurs at dry conditions This corrosion occurs at wet conditions in
presence of an electrolyte medium

Corrosion is uniform Not uniform, the anodic area is small, pitting is

frequent

It is slow process It is a rapid process

It involves direct chemical attack of metal
It involves the formation of large number of
by environment electrochemical cells.
It is explained by absorption mechanismExplain by mechanism of electrochemical
reactions
Corrosion products are produced at the Corrosion at anode, and corrosion products
place where corrosion takes place occurs at cathode.

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Types of Corrosion:

Galvanic corrosion: When two dissimilar metals are connected and jointly exposed to the
corrosive atmosphere the metal higher in the electrochemical series becomes anodic and
undergoes corrosion.
Ex: When Zn and Cu are connected and exposed to corroding atmosphere Zn becomes anodic
because of its higher oxidation potential or higher position in the electrochemical series. Zn
undergoes oxidation and corroded, whereas Cu undergoes reduction and protected. The
electrons released by Zn reach Cu through the metal.

Anodic metal:

Cathodic metal:

Galvanic corrosion

More examples: Zn and Ag, Fe and Cu constitute galvanic couple

Galvanic corrosion can be minimized by
1. Avoiding galvanic couples.
2. Providing an insulating material between two metals.

Waterline corrosion: The concentration of O2 above the water surface is greater than that
under the surface when water is stagnant in a steel tank. This generates an oxygen
concentration cell. In this cell the metal just above the water level is cathodic with respect to
the metal below the water level.
Corrosion occurs at anodic part, the metal just below the water level. The cathodic area is completely
unaffected by corrosion.

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Water line corrosion occurs just underneath the meniscus and water level

Pitting Corrosion: Consider a drop of water resting on the surface of metal, the metal surface
which is covered by the drop has low oxygen concentration and thus acts as an anode and suffers
corrosion. The uncovered metal surface due to high O2 concentration acts as cathode.

Pitting Corrosion

At anode:

At Cathode:

Formation of small anodic areas and large cathodic areas setup differences of potential at
localized spots to pit, this produces corrosion current. Pitting of the metal occurs when there
is a break in the protective layer. Pitting corrosion is a non uniform corrosion resulting in the
formation pits, cavities and pin-holes in the metal. Once a small pit is formed the rate of
corrosion will be increased.
Factors influencing corrosion:
Since corrosion is a process of destruction of metal surface by its environment, the two
factors that govern the corrosion process are:
(a) Nature of metal (b) Nature of the corroding environment

(a) Nature of the metal:

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(i)Position in galvanic series:
When two metals are in electrical contact in presence of an electrolyte, the metal with higher
oxidation potential suffers corrosion. The mined by the difference in the position of the
metals. The grater is the potential difference the faster and higher is the corrosion.
(ii) Over voltage:
When a metal say Zn is placed in 1N H2SO4 it under goes corrosion forming a film and
evolving hydrogen gas, the initial rate of corrosion is slow because of high over voltage
(0.7V) of the zinc metal which reduces the effective electrode potential to a small volume. If
a few drops of CuSO4 are added some copper gets deposited on the zinc metal, forming
minute cathodes, where hydrogen over voltage reduces to 0.33V. The reduction in over
voltage of corroding metal accelerates the corrosion rate.
(iii)Relative areas of the anodic and cathodic parts:
Smaller the area of anode compared to cathode will lead to faster corrosion of anode. It is
because the corrosion current at anode and at cathode will be same. But for small anodic area
the current density will be large at anode and larger cathodic area will demand more electrons
which will be fulfilled by fast reaction at anode (oxidation), i.e. rapid corrosion.
(iv)Purity of metal:
Impurities in a metal generally form Minute or tiny electrochemical cells and the anodic parts
get corroded. For example, zinc metal containing impurity (such as Pb or Fe) undergoes
corrosion of zinc, due to the formation of local electrochemical cells.
(v) Nature of surface film:
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. According to
Pilling- Bedworth rule the volume of oxide film is greater than metal from which metal oxide
formed, then the film is protective.
Ex: The specific volume ratios of W, Cr and Ni are 3.6, 2.0 and 1.6 respectively. Hence, the
rate of corrosion is least in Tungsten (W).
(vi) Physical state of metal:
The rate of corrosion is influenced by physical state of the metal .The smaller the grain-size
of the metal or alloy, the greater will be its solubility and hence, greater will be its corrosion.
(vii)Passive character of metal:
Metals like Ti, Al, Cr and Ni are passive they exhibit much higher corrosion resistance, due
to the formation of highly protective on the metal. Moreover the film is self healing nature.
Thus corrosion resistance of stainless steel is due to passive character of Cr.
(viii)Volatility of corrosion products: If the corrosion product is volatile (MoO3), it
volatilizes as soon as it is formed, thereby leaving the underlying metal surface exposed for
further attack. This causes rapid and continuous corrosion.
(ix)Solubility of corrosion products:
In electrochemical corrosion, if the corrosion product is soluble in the corroding medium,
then corrosion proceeds at a faster rate. On the contrary, if the corrosion product is insoluble
in the medium are thereby suppressing further corrosion.

2. Nature of the corroding environment:

(i) Temperature:
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With increase of temperature of environment, the reaction as well as diffusion rate increase,
thereby corrosion rate is generally enhanced.
(ii)Humidity of air:
Greater is the humidity, greater will be the rate and extent of corrosion. This is due to the fact
that moisture acts as a solvent for O2, H2S, SO2, NaCl etc. To furnish the electrolyte essential
for setting of a corrosion cell.
Ex: 1) Atmospheric corrosion of iron (Fe) is slow in dry air compared to moist air.
2) Gases like H2S and SO2 increase the acidity of the medium by their dissolution in water
and hence increase the corrosion rate.
(iii) Presence of impurities in atmosphere:
Atmosphere, in the vicinity of industrial areas, contains corrosive gases like CO2, H2SO4 and
fumes of HCl, H2 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.
(iv) Nature of ions present in the medium:
Presence of anions like silicate in the medium leads to the formation of insoluble reaction
products (e.g., silica gel), which inhibit further corrosion. On the other hand, chloride ions, if
present in the medium destroy the protective and passive surface film.
(v) Conductance of the corroding medium:
Due to presence of salts and water in earth, it is of conducting nature. More conductance
leads to more stray current and hence fast corrosion. Dry sandy soil is less conducting and
hence less corrosion, while mineralised clay soil is more conductance hence more corrosion
occurs.
(vi) Amount of oxygen in atmosphere:
As the percentage of oxygen in atmosphere increases, the rate of corrosion also increases due
to the formation of oxygen concentration cell. The decay of metal occurs at the anodic part
and cathodic part of the metal is protected.
At anode:

At cathode:

Net reaction:

(vii)

Velocity of ions which flow in the medium:

As the velocity of the diffusion of ions in the medium increases, the rate of corrosion
increases.
(viii) pH value of the medium:
Generally, acidic media (i.e., pH <7) are more corrosive than alkaline and neutral media.

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[Link] Nature of Metal Nature of environment

1 Position in the Galvanic series Temperature

2 Over voltage Humidity of air

3 Relative areas of the anode and Presence of impurities in atmosphere

cathode parts

4 Purity of metal Nature of ions present in the medium

5 Nature of the surface film Conductance of the corroding medium

6 Physical state of metal Amount of oxygen in atmosphere

7 Passive character of metal Velocity of ions which flow in the medium

8 Volatility of corrosion product pH value of the medium

9 Solubilities of corrosion product

CORROSION CONTROL METHODS:

Some of the corrosion control methods are described as follows:
 Proper Designing
 Cathodic Protection
 Using Pure metal
 Using Metal alloys
 Modifying the Environment
 Use of Inhibitors
 Application of Protective coatings

Cathodic protection:
The method of protection given to a metal by forcibly making it to behave like a cathode is
called cathodic protection. There are two types of cathodic protection.
1) Sacrificial anodic protection
2) Impressed current cathodic protection

1) Sacrificial anodic protection: In this method of protection, the metallic structure to be

protected called “base metal” is connected to more anodic metal through a wire, so that all
the corrosion is concentrated at the more anodic metal. As the more anodic metal is sacrificed
in the process of saving base metal from corrosion. Hence, it is known as sacrificial anode.
The corroded sacrificial anode block is replaced by a fresh one.
Metals commonly used as sacrificial anodes are Zn, Al, Mg and their alloys. Mg is used in
high resistivity electrolytes such as soils due to its most negative potential and it can provide
highest current output.

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Applications: Important application of this technique are

a) Protection of underground cables and pipelines from soil corrosion

b) Protection of ships and boat hulls from marine corrosion. Sheets of Mg or Zn are
hung around the ship hull, these sheets being anodic to corrosion so these sheets get
corroded, when consumed completely, these are replaced by fresh one

c) The formation of rusty water is prevented by the insertion of Mg sheets or rods into
domestic water boilers or tanks.

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Disadvantages of cathodic protection:

[Link] cathodic protection may be efficient in protecting a pipeline but it may increase the
corrosion of the adjacent pipelines or metal structure because of stray currents.
[Link] investment and maintenance costs are more.
[Link] care must be taken that the metal is not over protected.

Impressed current cathodic protections:

In this method current from an external source is impressed (applied in the opposite direction)
to nullify the corrosion current. Thus the anodic corroding metal becomes cathodic and
protected from corrosion.

The anode may be either an inert metal or one which deteriorates and will have to be replaced
periodically. The commonly used anodic materials are graphite, carbon, stainless steel, scrap
iron, high silica iron and platinum. The anode is buried in back fill such as gypsum to
increase the electrical contact between itself and the surrounding soil.

Application: This protection method is useful when electrolyte resistivity and current
requirements are high. It is well suited for large structures and long-term applications.
This protection technique is employed in the case of open water box coolers, water tanks,
buried pipe-lines, marine pipes etc.

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Surface coatings – methods of application on metals:

The common method of a protection of a metal from its surroundings is applying a protective
coating on the surface of the metal. The coated surface isolates the metal from its corroding
environment. The requirement of this type of protection are
a) The coating applied must be chemically inert to the environment.
b) Coating must prevent the penetration of the environment to the metal.
Function of the protective coating
1) To protect the metal from corrosion
2) To impart esthetic sense to the metal surface.
3) To impart specific mechanical and physical properties
4) To give oxidation resistance and thermal insulating properties.

Metallic coatings
Metallic coatings are produced by coating of one metal on the surface of another metal. The
metal which is protected is called base metal and the metal which is coated on the surface of
the base metal is called coating metal.
Metallic coatings are two types.

(i) Anodic coatings: These are produced from coating-metals, which are “anodic” to the base
metal. For example, coating of Zn, Al and Cd on steel are anodic, because their electrode
potentials are lower than that of the base metal, iron. If any pores, breaks or discontinuities
occur in such an anodic coating, a galvanic cell is formed between the coating-metal and the
exposed part of base metal, In case of galvanized steel, zinc, the coating-metal (being anodic)
is attacked ; leaving the underlying cathodic metal (iron) unattacked. So, zinc coating protect
iron „sacrificially‟.

(ii) Cathodic coatings: These are produced from coating-metals, which are “cathodic” to the
base metal. These are obtained by coating a more noble metal (i.e., having higher reduction
electrode potential) than the base metal. Cathodic coating provides effective protection to the
base metal only when they are completely continuous and free from pores, breaks or
discontinuities. If such coatings are punctured, much more corrosion damages can be done to

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the base metal than to metal without it. For example, a tin-coating on a sheet of iron provides
protection only as long as the surface of the metal is completely covered.

[Link] Anodic coating Cathodic coating

1 Protects the underlying base metal Protects the underlying base metal, due
„sacrificially‟. to its noble character and higher
corrosion-resistance.
2 Electrode potential of coating metal is Electrode potential of coating metal is
lower than that of the base metal. higher than that of the base metal.
3 If pores, breaks or discontinuities occur If pores, breaks or discontinuities occur
in such a coating, the base metal is not in such a coating, corrosion of the base
corroded, till all the coating metal is metal is speeded up.
consumed.
4 Coating of Zn on iron is an example. Coating of Sn on iron is an example.

Methods of applications of metallic coatings

Hot dipping:
o o
This is a method of coating a low melting metal such as Zn (m.p.=419 C), Sn (m.p.=232 C)
Pb, Al, etc., on iron, steel and copper which have relatively higher melting points. The base
metal is dipped in a molten bath of the coating metal which is covered by a molten flux layer
which cleans the base metal surface and prevents the oxidation of the coating metal. For good
adhesion of the coating metal on the surface of base metal, the base metal surface must be
very clean.
The most commonly used hot dipping methods are galvanizing and tinning.

Galvanizing:
It is a process of coating iron or steel sheets with a thin coat of Zn to prevent iron from
rusting.
Process:
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The base metal iron or steel sheet is cleaned by acid pickling method with Dil. H2SO4 for 15-
o
20 minutes at 60-90 C. The sheet is then washed well and dried. It is dipped in a bath of
o
molten zinc maintained at 425-435 C. The surface of the bath is kept covered with
ammonium chloride flux to prevent oxide formation. The sheet is taken out and excess Zn is
removed by passing it between a pair of hot rollers. Then the sheet is subjected to annealing
o
process at 650 C and cooled slowly. An alloy of iron and zinc were formed at the junction of
the base metal and coating metal.

Applications: It is mostly used to protect iron used for roofing sheets, wires, pipes, nails,
bolts, screws, buckets and tubes.
Galvanizing utensils cannot be used for preparing and storing food stuffs especially acidic in
nature, because zinc dissolves to form highly toxic or poisonous compounds.

Tinning:
The process of coating a layer of tin on iron is called tinning.
Process:
The iron article is first pickled with dil. H2SO4 to remove impurities like dust, rust present on
the surface. It is then passed through a bath containing molten tin maintained at 250-290°C.
The surface of the molten tin is covered with ZnCl2 flux. The excess of tin is removed by
passing the tin coated article through pair of hot rollers. Then the hot tin coated article is
passed through a palm oil bath to protect the tin coated surface against oxidation.

Uses:
Tin coated utensils are used for storing food products.

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Cementation (Diffusion coating):
It is a process of obtaining a coating by heating the metal object in a powder of the coating
metal. Diffusion of the coating metal in to the base metal resulting the formation of layers of
alloy of varying composition.
Sherardizing: Coating zinc on iron base metal is called Sherardizing. The iron article to
be coated is cleaned by acid pickling process and rotated for 2-3 hours in a drum containing
zinc dust at 350-370°C. During this process zinc diffuses into iron forming iron zinc alloy.
Sherardizing is used for coating small steel articles like bolts, screws, nuts, washers and
valves.
Colorising:
It is a method of coating aluminium on the surface of iron by cementation. The object is sand
blasted and heated in the presence of hydrogen in a tightly packed mixture of Aluminium
powder, alumina (Al2O3) and a trace of NH4Cl as flux. The layer formed has the approximate
composition of Al2Fe3. Colorising is used for the protection of furnace parts.
Chromising:
The base metal is heated with a mixture of 55% Cr and 45% of alumina powder to 1300-
1400°C for 3-4 hours. A mixture of volatile chromous chloride and hydrogen with steel parts
produce the protective layer of chromium diffused in to iron surface. Chromising is used for
the protection of turbine blades.
Siliconising:
Coating silicon on the surface of molybdenum by cementation is called siliconising.
Silicon tetra chloride is used as a coating metal.

Electroplating or Electrodeposition:
The process of depositing the coating metal on the surface of base metal/non-metal by
electrolysis is called electroplating.

The base metals are inferior or anodic to the coating metal and electrolyte is the solution
containing the metal ions to be deposited on the base metal. The base metal is made cathode
and the coating metal is made anode or an inert material of good electrical conductivity is
also used as an anode. A direct current is passed through the electrolytic solution. If anode is
made of graphite, the electrolytic salt is added continuously to maintain the proper coating
metal ion concentration in the electrolyte bath.

The article to be electroplated is subjected to solvent cleaning by trichloroethylene to remove

oil, greases etc. then it is subjected to acid pickling with [Link] or dil.H2SO4 to remove any
scales, oxides etc. the cleaned article is made cathode of the electrolytic cell and the anode
can be made of the pure coating metal or graphite. The electrodes were dipped in the salt
solution of the coating metal, which acts as an electrolyte. When direct current is passed, the
coating metal ions migrate to the cathode and deposit on the base metal article in the form of
a thin layer. For brighter and smooth deposits, conditions like low temperatures, medium
current density, and low metal ion concentration are used.
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Electroplating of copper on iron article. The following are maintained

1) Electrolytic bath solution – Copper sulphate
2) Temperature maintained – 40-70°C (Low temperature for brighter and smooth surface)
3) Current density – 20-30 mA/cm2 (medium current density for high efficiency)
4) Anode- copper pellets or Graphite
5) Cathode- Base metal article.
Application: Electroplating is a most important and frequently used technique in industries to
produce metallic coatings. Both metals and non-metals can be electroplated. In metals the
electroplating increase resistance to corrosion, chemical attack, hardness, wear resistance and
surface properties. In non-metals electroplating increases strength and decorates the surface
of non-metals like plastics, wood, glass etc.

Electroless plating(Autocatalytic Process):

The method of deposition of a metal from its salt solution on a catalytically active surface by
a suitable reducing agent without using electrical energy is called electroless plating.

This process is also called chemical plating or autocatalytic plating.

The metallic ions (M+) are reduced to the metal with the help of reducing agents.
When the metal(M) is formed, it gets plated over a catalytic surface.

Metal ion(M+) + Reducing Agent Metal deposit + Oxidised product

Electroless plating of Ni:

It is an auto-catalytic chemical technique used to deposit a layer of nickel phosphorus
or nickel-boron alloy on a solid work piece, such as metal or plastic. The process
depends on the presence of a reducing agent.
It involve the following features
Pretreatment and activation of the surface: The surface to be plated is activated by
treatment with organic solvents or alkali, followed by acid treatment

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Composition of Bath:
Coating solution- NiCl2 solution
Reducing agent- Sodium hypophosphite (NaH2PO2.H2O)
Buffer- Sodium acetate
Complexing agent- Sodium succinate
Optimum PH- 4.5
Optimum temperature – 93°C

Reactions:
Ni+2 2e- Ni ( Cathode)

H2PHO2- H2 O H2PHO3- 2H+ 2e- (anode)

Net Reaction: Ni+2 H2PHO2- H2 O Ni H2PHO3- 2H+

Advantages of Electroless plating:

1. Electrical energy is not required.

2. Even intricate parts (of irregular shapes) can be plated uniformly
3. There is flexibility in plating volume and thickness.
5. Bright finishes can be obtained.
6. Plating on articles made of insulators (like plastics) and semiconductors can easily be
carried out.
7. Electroless plated Ni objects has better corrosion resistance, deposits are pore free, hard
and wear resistant.

Applications:
1) They are used in electronic industry for fabricating printed circuits and diodes.
2) It is used in domestic as well as automotive fields (eg. jewellery, tops of perfume bottles).
3) Its polymers are used in decorative and functional works.
4) Its plastic cabinets are used in digital as well as electronic instruments.

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