UNIT (III): Electrochemistry and corrosion

Electrode, electrode potential, galvanic cell, cell reactions and cell notation, cell EMF, types of
electrodes (Calomel electrode and Quinhydrone electrode), Determination of PH using
quinhydrone electrode. Nernst equation, Numerical problems.
BATTERIES: Introduction to cell and battery, Primary (lithium cell) and secondary cells, (lead-
Acid cell, and Lithium ion cells). Fuel cells – Methanol – Oxygen fuel cell, advantages and
engineering applications of fuel cells.
Corrosion: Introduction, types of corrosion: chemical and electrochemical corrosion, factors
affecting the rate of corrosion: nature of the metal, position of metal in galvanic series, purity of
metal, nature of corrosion product, nature of environment: effect of temperature, effect of pH,
humidity. Corrosion control methods: Cathodic protection: sacrificial anode method and
impressed current cathode method. Protective coatings: metallic coatings (anodic and cathodic),
methods of application on metals- electroless plating (of Ni).

Electro chemistry is a branch of chemistry which deals with the transformation of electrical energy
into chemical energy or chemical into electrical energy.

Electrode:

An electrode is an electrical conductor used to make contact with a nonmetallic part of a circuit
(e.g. a semiconductor, an electrolyte, a vacuum or air).

Single electrode potential (or) electrode potential:

It is a measure of the tendency of the metal electrode to lose or gain electrons, when it is in contact
with its own salt solution. Single electrode potential is also known as half-cell potential.

Electro chemical cell (Galvanic cell):-

Galvanic cell is a device in which chemical energy is converted into electrical energy. This cell is
made up of two half cells. One is anodic half-cell. The other is catholic half-cell. The electrode
where oxidation occurs, is called anode; while the electrode where reduction occurs, is called
cathode. Since electrons are produced on anode, this electrode is rich in electrons and hence is also
negative (-) electrode. Since cathode gets electrons from the anode through external circuit. This
electrode is deficient in electrons and is also called positive (+) electrode.

Daniel cell is an example for galvanic cell. It consists of zinc electrode dipped in ZnSO4 solution
and a copper electrode dipped in CuSO4 solution. Both the half cells are connected externally by
metallic conductor. The two solutions are separated by a salt bridge. The electrode reactions in
Daniel cell are

At anode (oxidation reaction takes place)

Zn Zn+2 + 2e-

At cathode (reduction reaction takes place)

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 Cu+2 + 2e- Cu

Cell (Redox) reaction

Zn + Cu+2 (aq) Zn+ 2 (aq) + Cu

Representation of a galvanic cell (cell notation)

According to present conventions, a galvanic cell is represented by keeping in view the following
points:

(i) The anode is written on the left hand side while the cathode is written on right side.

(ii) The anode is written with the metal first and then the electrolyte .The two are separated by a
vertical line or semicolon or colon. 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 brackets.

Ex: Zn | Zn 2+ (or) Zn; Zn2+ (or) Zn: Zn2+

(iii) The cathode is written with electrolyte first and then the metal both are separated by vertical
line or semicolon or colon. The electrolyte may be represented by the formula of the whole

2
compound or by ionic species. Additional information regarding concentration may also be
mentioned in brackets.

Ex: Cu2+ | Cu (or) CuSO4; Cu (or) Cu2+: Cu

(iv) The two half cells are connected by a salt bridge which is indicated by two parallel (vertical)
lines.

Zn | ZnSO4 (1M ) ║ CuSO4 ( 1M ) | Cu

Electro motive force (emf):-

The difference of potential which causes flow of electrons from an electrode of lower reduction
potential (anode) to an electrode of higher reduction potential (cathode) is called electro motive
force (emf) of the cell. (Or)

It is also defined as the potential difference between the two electrodes of a galvanic cell which
causes the flow of current from an electrode with higher reduction potential to the electrode with
lower reduction potential.

Calculating the emf of a cell

The emf of a cell can be calculated from the half-cell potentials of the two cells (anode and cathode)
by using the following formula
ECell = ECathode − EAnode = ER − EL

Where ER and EL are the reduction potentials of the right-hand and left-hand electrodes
respectively. It may be noted that absolute values of these reduction potentials cannot be
determined. These are found by connecting the half-cell with a standard hydrogen electrode whose
reduction potential has been arbitrarily fixed as zero.

In a galvanic cell the electrode having higher value of Eo acts as cathode (RHS electrode) and the
electrode having lower value of Eo acts as anode (LHS electrode). Ecell should be positive otherwise
it will not be feasible in the given direction

Zn | ZnSO4 ║ CuSO4 | Cu ECell = +1.1 V (feasible)

CuSO4 | Cu ║ Zn | ZnSO4 ECell = −1.1 V (not feasible)

Standard emf of a cell

The value of emf varies with the concentration of the reactants and products in the cell and the
temperature of the cell. When the emf of a cell is determined under standard conditions, it is called
the standard emf. The standard conditions are (a) 1 M solutions of reactants and products; and (b)
temperature of 25°C. Thus standard emf may be defined as: the emf of a cell with 1 M solutions

3
of reactants and products in solution measured at 25°C. Standard emf of a cell is represented by
the symbol E°. With gases 1 atm pressure is a standard condition instead of concentration.

Measurement of single electrode potential:

It is impossible to determine the value of a single electrode potential. But we can always measure
the potential difference between two electrodes using a potentiometer, by combining the two
electrodes to form a cell.

Electrode potential is measured against reference electrode i.e. standard hydrogen electrode (SHE).
The reference electrode potential of standard hydrogen electrode [Pt, H2 (1atm), H+ (1M)] is taken
as zero. To measure the electrode potential of any electrode, it is connected to SHE and the system
acts like a cell. The electro motive force (EMF) of the cell is measured with the potentiometer.
Since the electrode potential of the SHE is zero, the reading of the potentiometer will be the
electrode potential of the electrode.

Standard oxidation potential (SOP):

It is the potential generated by an oxidation at anode compared to the standard hydrogen electrode
25 oC, 1 atmosphere and a concentration of 1M.

Standard reduction potential (SRP):

It is the potential generated by a reduction at cathode compared to the standard hydrogen electrode
25 oC, 1 atmosphere and a concentration of 1M.

Origin of electrode potential:

When a metal M is dipped in its salt solution, one of the following reactions occurs depending on
the metal:
1. Positive metal ions pass into the solution:
M M+n + ne- (oxidation)
Eg. When Zn rod is dipped in ZnSO4 solution, Zn goes into solution as Zn+2. The electrons attach
to Zn rod, giving it a negative charge. The negative charge on the rod attracts positive ions from
solution. Thus a double layer of ions is formed close to the rod.
2. Positive ions from the solution deposit over the metal.
M+n + ne- M (reduction)
When Cu rod is dipped in CuSO4 solution, Cu+2 ions from the solution deposit on metal rod. They
attract negative ions from solution. Thus a double layer of ions is formed close to the metal rod.

Due to above processes, a state of equilibrium is established between the metal atom M and its
ions M+n.

4
At equilibrium negative or positive charge developed on the metal, attracts the positively or
negatively charged ions respectively present in the solution. Hence an Electrical Double Layer is
formed at the interface, called Helmholtz Electrical Double Layer. As a result a potential difference
is set up between the metal and the solution. At equilibrium the potential difference between a
metal and the solution remains constant and is known as electrode potential.

Salt bridge: It consists of a U tube filled with a saturated solution of KCl, KNO3 or NH4NO3 in
agar-agar gel. It connects the two half cells and performs the following functions.

• Completes the circuit.

• Maintains electrical neutrality in the two compartments by migration of ions through the porous
material thus ensures the chemical reactions proceed without hindrance.

• It provides path for the flow of electrons between two half cells.

• Prevents mixing of the electrode solutions.

• It eliminates the liquid junction potential.

Electrochemical series

The arrangement of different electrodes in order of their increasing values of standard reduction
potential is called electrochemical series. Or
A series in which elements are arranged in the ascending (increasing) order of their standard
reduction potential is called electrochemical series.

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Nernst equation
Consider a general reaction:

Free energy change for reversible reaction is given by

ΔG = ΔGo + RTlnQ
For a reversible reaction the electrical energy is produced by decreasing the free energy of the
system i.e., ΔG = − nFE and ΔGo = − nFEo (Where, ΔG = free energy change, ΔGo = standard
free energy change, E = electrode potential; Eo = standard electrode potential, n = number of
electron change; F is Faraday = 96,500 Coulomb). Q is the reaction quotient of the concentration
of the products and reactants, i.e.,

[𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠] [𝑀]
𝑄= =
[𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠] [𝑀]+𝑛

[𝑀]
− 𝑛𝐹𝐸 = −𝑛𝐹𝐸 𝑜 + 𝑅𝑇𝑙𝑛
[𝑀+𝑛 ]

Dividing both sides by –nF

𝑅𝑇 [𝑀]
𝐸 = 𝐸𝑜 − 𝑙𝑛 +𝑛
𝑛𝐹 [𝑀 ]

2.303𝑅𝑇 1
𝐸 = 𝐸𝑜 − 𝑙𝑛 +𝑛
𝑛𝐹 [𝑀 ]

2.303𝑅𝑇
𝐸 = 𝐸𝑜 + 𝑙𝑜𝑔[𝑀+𝑛 ]
𝑛𝐹

We know R = 8.314 J K-1 mol-1 and F = 96,500 Coulomb

If temperature is 298 K then

0.0591
𝐸 = 𝐸𝑜 + 𝑙𝑜𝑔[𝑀+𝑛 ]
𝑛

This expression is known as Nernst’s equation for electrode potential at 298 K.

Nernst’s equation for cell potential

Let us consider a general reaction

Applying Van’t Hoff reaction isotherm, ΔG = ΔGo + RTlnQ

6
For a reversible reaction the electrical energy is produced by decreasing the free energy of the
o
system i.e., ΔG = − nFEcell and ΔGo = − nFEcell (Where, ΔG = free energy change, ΔGo = standard
o
free energy change, Ecell = cell potential; Ecell = standard cell potential, n = number of electron
change and F is Faraday = 96,500 Coulomb). Q is the reaction quotient of the concentration of the
products and reactants, i.e.,

[Product] [C]c [D]d

Q= =
[Reactant] [A]a [B]b

o [C]c [D]d
− nFEcell = −nFEcell + RTln
[A]a [B]b

Dividing both sides by –nF

o RT [C]c [D]d
Ecell = Ecell − ln
nF [A]a [B]b

o 2.303RT [C]c [D]d

Ecell = Ecell − log a b
nF [A] [B]

This expression is known as Nernst’s equation for cell potential at any given temperature.

We know R = 8.314 J K-1 mol-1 and F = 96,500 Coulomb

If temperature is 298 K then

o 0.0591 [C]c [D]d

Ecell = Ecell − log a b
n [A] [B]

This expression is known as Nernst’s equation for cell potential at 298 K.

The Nernst equation shows now the cell potential depends on the concentration or molarity of what
the components are in the cells.

Applications

1. To find the electrode and cell potentials

Electrode and cell potential can be calculated under a given set of conditions by using
Nernst equation.
2. To find the equilibrium constant (Keq) for the cell reaction
At equilibrium, Ecell = 0 and Q = Keq
o 2.303RT
0 = Ecell − logK 𝑒𝑞
nF

7
At 298 K,
o
𝑛Ecell
logK 𝑒𝑞 =
0.0591

The equilibrium constant for the redox reaction can be calculated from the standard
electrode potential.
3. To find the pH of an unknown aqueous solution
pH of an aqueous solution can be measured by using different electrodes such as hydrogen
electrode, quinhydrone or glass electrode.
Ecell = 0.0591𝑝𝐻 (When hydrogen electrode coupled with SHE)

4. Determination of the valence of an ion

5. To find the solubility/solubility product of a sparingly soluble salt

Types of Electrodes

The electrodes of known potential, with reference to which the potential of any other electrode can
be measured, are called reference electrodes.
The Reference Electrodes can be classified in to two types
i) Primary reference electrodes Ex: Standard hydrogen electrode
ii) Secondary reference electrodes Ex: Calomel and Ag/AgCl electrodes
The standard hydrogen electrode (SHE) is not the most convenient standard electrode to use in the
laboratory. The gas has to be carefully controlled and hydrogen gas can form explosive mixtures
with air.
Any other electrode system whose potential has been determined relative to the SHE can also be
used as Secondary reference electrode.

Calomel electrode:

It is the mercury-mercurous chloride electrode. It is the most

commonly used secondary standard reference electrode. The
potential of the calomel electrode depends on the concentration
of KCl solution taken in the half-cell. Thus for 0.1N KCl solution
(Decinormal calomel electrode) emf at 298K is 0.3335 V; for 1N
solution (Normal calomel electrode) emf at 298K is 0.2810 V; and
for saturated KCl solution (Saturated calomel electrode) emf is
0.2422 V.

Construction: Saturated calomel electrode

It consists of a tube in the bottom of which is a layer of mercury, over
which is placed a paste of Hg + Hg2Cl2. The remaining portion of cell is filled with a saturated
solution of KCl. A platinum wire, dipping into the mercury layer, is used for making electrical
contact. The side-tube containing KCl solution provides the salt bridge which connects the
electrode to any other electrode. The saturated calomel electrode is formulated as: Hg (l), Hg2Cl2

8
(s), KCl (saturated solution). The calomel electrode acts as both anode and cathode depending
upon the other electrode used. The calomel electrode involves the following reaction

Anode Cathode:
Hg (l) | Hg2Cl2 (s), KCl (saturated solution) KCl (saturated solution), Hg2Cl2 (s) | Hg
(l)

Advantages of Calomel Electrode:

1. It is simple to construct.
2. The electrode potential is reproducible and stable.
3. It is used as a reference electrode.

Quinhydrone electrode

The quinhydrone (or quinone-hydroquinone) electrode is a type of redox electrode which can be
used to measure the hydrogen ion concentration (pH) of a solution in a chemical experiment.
Quinhydrone is a molecular compound which gives equimolar amounts of quinone and
hydroquinone in solution. Electrode system may be represented as Pt | QH2, Q. The potential
developed is measured against a hydrogen electrode or calomel electrode. The reduction potential
for the standard quinhydrone electrode at 25 oC is 0.6994 V.
Quinhydrone electrode can very easily be set up by adding a pinch of quinhydrone powder (a
sparingly soluble solid) to the experiment solution with stirring, until the solution is saturated and
a slight excess of it remains undissolved. Then, indicator electrode (platinum) is inserted in it. It
involves the redox reaction between quinone (Q) and hydroquinone
(QH2).
The quinhydrone system involves the following reactions

At anode (Pt | QH2, Q)

9
At cathode (Pt | Q, QH2)

Thus, when a platinum electrode is immersed in a solution containing quinhydrone, a potential is

established, the value of which is given by

o
2.303RT [Q𝐻2 ]
EQ, 𝐻2 Q = EQ,Q𝐻 − log
2
2F [𝑄] [𝐻 + ]2

and if quinone and hydroquinone are taken in equimolar concentrations, then [Q] = [QH2]

o
2.303RT 1
EQ,QH2 = EQ,QH − log + 2
2
2F [H ]

o
2.303RT
= EQ,QH + log[H + ]
2 F

= 0.6994 – 0.0591pH

Merits
(1) Quinhydrone electrode is easily set up by simply immersing a platinum strip in the test solution.
(2) The pH values are very accurate even in the presence of oxidising ions which interfere with
the working of a hydrogen electrode.
Demerits
It does not give satisfactory results for solutions whose pH is more than 8.5 due to the ionisation
or oxidation of hydroquinone.

Determination of PH using quinhydrone electrode

To determine pH of unknown solution the quinhydrone electrode is combined with secondary

reference electrode such as calomel electrode and the e.m.f., of the cell so formed is determined
potentiometrically. The complete cell may be represented as.
Hg(l) | Hg2 Cl2 (S), Saturated KCl || H+ (unknown), Q, H2Q | Pt.

𝐸𝑐𝑒𝑙𝑙 = EQ, 𝐻2 Q − 𝐸𝑆𝐶𝐸

o
𝐸𝑐𝑒𝑙𝑙 = EQ, H2 Q – 0.0591pH − 𝐸𝑆𝐶𝐸

o
EQ, H2 Q − 𝐸𝑐𝑒𝑙𝑙 − 𝐸𝑆𝐶𝐸
𝑝𝐻 =
0.0591

10
Battery is an electrochemical cell or often several electrochemical cells connected in series that
can be used as a source of direct current at a constant voltages.

Classification of Batteries

Batteries are classified mainly into two types as follows.

a) Primary; b) Secondary batteries

a. Primary battery:
The battery in which the cell reaction is not reversible. Thus when the reactants have been
converted to products, no electricity is produced and the cell becomes dead and cannot be used
after that. These cannot be recharged. These batteries are used as a source of dc power. Eg:
Leclanche battery, dry battery, alkaline battery, lithium battery, lemon battery etc.

b. Secondary Battery:
The battery in which the cell reaction is reversed by passing direct current in opposite direction.
These batteries are chargeable and can be used again and again. During discharging the cell acts
like voltaic cell converting chemical energy into electrical energy. During charging the cell acts
like electrolytic cell by converting electric energy into chemical energy, hence these batteries are
called as storage battery. They are used as source of dc power used to supply large, short-term
repetitive power requirement such as automotive and air plane battery. Eg: Lead-Acid battery,
Nickel-Cadmium battery, lithium ion battery and etc.

Lithium batteries:
The batteries having lithium anodes are called lithium batteries, irrespective of the cathode used.
Eg: Li-MnO2.
Li-MnO2 Battery:
It is a primary battery and is not rechargeable. It consists of a lithium anode and a MnO2 cathode.
These systems may have solid or liquid electrolyte. In general, the electrolyte is a mixture of
propylene carbonate and 1,2-dimethoxy ethane. The cathode MnO2 should be heated to greater
than 300 oC to remove water before incorporating it in the cathode. This is very important to
improve the efficiency of the cell.
Working:
At anode, oxidation of lithium takes place producing
Li+ ions. Li+ ions move into the electrolyte and
electrons move into the external circuit to reach the
cathode. At cathode, MnO2 is reduced from +4
oxidation state to +3 states to give Li+MnO2.

11
It has high voltage (3.0 V), high energy density, and good performance over a wide range of
temperatures (-20 to 55 oC), long shelf life and low cost. Thus it is used in electronic watches,
calculators, safety and security devices, automatic cameras, toys and many consumer electronic
devices.

Storage cell:
A storage cell is the one, which can operate both as a voltaic cell and as an electrolytic cell. When
it acts as a voltaic cell, it supplies electrical energy and becomes “run down”. When it is recharged,
the cell operates as an electrolyte cell.
Eg: Lead-acid battery

Lead-acid battery:
Construction:
A lead-acid storage battery consists of a
number of voltaic cells connected in
series. In each cell, the anode is made of
lead. The cathode is made of lead
dioxide. Number of Pb plates and PbO2
plates are connected in parallel. Plates
are separated from adjacent ones by
insulators like rubber or glass fiber. This
arrangement is immersed in an
electrolyte of about 38% H2SO4 with
specific gravity 1.3 g/cm solution. The
cell may be represented as:
Pb/PbSO4/H2SO4(aq) /PbO2/ PbSO4.

Working:
Discharging:

When the battery is used for

supplying electrical energy, it is
said to be discharged. In the
process, lead electrode gets
oxidized to Pb+2 ions which then
combine with SO4-2 ions to form
PbSO4. The electrons released from
anode are utilized at the cathode to
reduce PbO2 to Pb+2 ions. These
Pb+2 ions also combine with SO4-2
ions to form PbSO4. The reaction
occurring at the electrodes and cell
are as follows.

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Charging:

During discharging, PbSO4 is

precipitated at both the electrodes.
When PbSO4 covers completely
both the electrodes, the cell stops
working. For further use it needs
to be recharged. The cell can be
recharged by connecting it to an
external current source so as
reverse the cell reaction. This is
possible as PbSO4 formed stick to the electrodes and is positioned to gain or lose electrons.

Applications:
Lead acid batteries are used for many purpose such as to supply current for electrical vehicles, gas
engine ignition, in telephone exchanges, railway trains, mines, laboratories, hospitals, broadcasting
stations, power stations and distribution works.

Lithium-ion battery (Li-ion battery)

A lithium-ion battery is a type of rechargeable battery in which lithium ions move from the
negative electrode to the positive electrode during discharge and back when charging.

Li-ion batteries use an intercalated lithium compound as one electrode material, compared to the
metallic lithium used in a non-rechargeable lithium battery. The electrolyte, which allows for ionic
movement, and the two electrodes are the constituent components of a lithium-ion battery cell.

Eg: LiCoO2

Lithium cobalt oxide [LiCoO2] battery:

Construction:

In Li-ion battery, lithium-doped graphite intercalation compound electrode is used as the anode
(LixC), while the cathode is made up with an intercalated lithium in layered cobalt oxide compound
(Li1-xCoO2). A porous polyethylene (or) polypropylene film is used as separator. A lithium salt in
an organic solvent is used as electrolyte.

13
Working:
During discharging, Li-ions are dissociated
from anode and migrate through electrolyte to
cathode. During charging, the reverse occurs.

Applications
Used in cell phones, laptops, portable LED
TV, portable audio device, power
backups/UPS and etc…

Fuel cell:

Fuel cells are the galvanic cells which converts chemical energy of fuels into electrical energy by
the combustion of fuels.
A fuel cell has two electrodes with catalysts and electrolyte. In this device fuel and oxidizing agents
are continuously and separately supplied to the respective electrodes at which they undergo redox
reaction to produce electrical energy. Fuel cells produce electrical energy as long as fuels are
supplied at respective electrodes.

Advantages of the Fuel cells:

a. They operate very silently.
b. Their power efficiency is high.
c. The cells have high energy density.
d. Space required for fuel cell is less.
e. Produce harmless byproducts.

14
 f. Produces direct current for a long time.

Methanol-Oxygen Fuel cell:

Construction:
It consists of anodic and cathodic compartments
and both the compartments contain platinum
electrode. Methanol containing H2SO4 is passed
through anodic compartments. Oxygen is passed
through cathodic compartments. Electrolyte
consists of sulphuric acid (3.7 M). A membrane is
provided which prevents the diffusion of methanol
into the cathode.
Working:
At anode, CH3OH undergoes oxidation to CO2
liberates electrons, the liberated electrons taken by
oxygen gets reduced into water with liberation of
energy at cathode. The cell potential is 1.21V at 25 oC.

Applications
1. Used in military applications.
2. Used in space crafts and submarines to get
electricity.
3. Used for large scale power production stations.

15
Numerical problems:

1. Calculate the electrode potential of Zn electrode dipped in 0.1N ZnSO4 solution

at 25 oC.

Solution:

Nernst’s equation for electrode potential at 298 K.

0.0591
𝐸 = 𝐸𝑜 + 𝑙𝑜𝑔[𝑀+𝑛 ]
𝑛

Zn+2 (aq) + 2e- Zn

E o 𝑍𝑛+2/𝑍𝑛 = −0.76 𝑉

Nernst equation
0.0591
E𝑍𝑛+2/𝑍𝑛 = E o 𝑍𝑛+2/𝑍𝑛 + 𝑙𝑜𝑔[𝑍𝑛+2 ]
2

0.0591
= - 0.76 + 𝑙𝑜𝑔[ 0.1]
2

= - 0.76 + 0.0295(-1)
= -0.76 - 0.0295
= - 0.7895 V

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2. Calculate the emf of the following cell:

Cd (s) | Cd2+ (0.001 M) || Cu2+ (0.1 M) | Cu (s) at 298K. The standard reduction
potential of cadmium and copper are −0.40 V and 0.34 V, respectively.

Solution:

At anode (oxidation reaction takes place)

Cd Cd+2 (aq) + 2e-

At cathode (reduction reaction takes place)

Cu+2 (aq) + 2e- Cu

Cell (Redox) reaction

Cd + Cu+2 (aq) Cd+ 2 (aq) + Cu

o 2.303RT [Cd+2 ]
Nernst equation Ecell = Ecell − log
nF [Cu+2 ]

R = 8.314 J K-1 mol-1 , T = 298 K, F = 96,500 Coulomb, n = 2

0.0591 0.001
Ecell = 0.74 − log
2 0.1
= 0.74 + 0.0591

= 0.7991 V

17
 Unit-III (part B)
Corrosion: Introduction, types of corrosion: chemical and electrochemical
corrosion, factors affecting the rate of corrosion: nature of the metal, position of
metal in galvanic series, purity of metal, nature of corrosion product, nature of
environment: effect of temperature, effect of pH, humidity. Corrosion control
methods: Cathodic protection: sacrificial anode method and impressed current
cathode method. Protective coatings: metallic coatings (anodic and cathodic),
methods of application on metals- electroless plating of Ni.

Metals and alloys are used as construction and fabrication materials in engineering. If the metals
or alloy structures are not properly maintained, they deteriorate slowly by the action of atmospheric
gases, moisture and other chemicals. This phenomenon of destruction of metals and alloys is
known as corrosion.

Corrosion is the deterioration or destruction of materials (metals and alloys) by chemical

interaction with their environment.

Example:
1. Rusting of iron, a layer of reddish scale and powder of oxide (Fe3O4) is formed on the surface
of iron metal.
2. A green film of basic carbonate [CuCO3 + Cu(OH)2] is formed on the surface of copper, when
it is exposed to moist-air containing carbon dioxide.

In nature, most metals are found in a chemically combined state known as an ore. All the metals
except gold, platinum and silver exist in nature in the form of their oxides, carbonates, sulphides,
sulphates, etc. The metals are extracted from their metallic compounds (ores). During the
extraction, ores are reduced to their metallic states by applying energy in the form of various
processes. In the pure metallic state, the metals are unstable as they are considered in excited state
(higher energy state). Therefore as soon as the metals are extracted from their ores, the reverse
process begins and form metallic compounds, which are thermodynamically stable (lower energy
state). Hence, when metals are used in various forms, they are exposed to environment, the exposed
metal surface begin to decay (conversion to more stable compound). This is the basic reason for
metallic corrosion.

The Consequences of Corrosion

The consequences of corrosion are many and varied and the effects of these on the safe, reliable
and efficient operation of equipment or structures are often more serious than the simple loss of a
mass of metal. Failures of various kinds and the need for expensive replacements may occur even
though the amount of metal destroyed is quite small. Some of the major harmful effects of
corrosion can be summarized as follows:

1
1. Reduction of metal thickness leading to loss of mechanical strength and structural failure or
breakdown. When the metal is lost in localized zones so as to give a crack like structure, very
considerable weakening may result from quite a small amount of metal loss.
2. Hazards or injuries to people arising from structural failure or breakdown (e.g. bridges, cars,
aircraft).
3. Loss of time in availability of profile-making industrial equipment.
4. Reduced value of goods due to deterioration of appearance.
5. Contamination of fluids in vessels and pipes.

Classification of Corrosion
The preferred classification is: Dry or chemical corrosion and wet or electrochemical corrosion.
Chemical Corrosion or Dry Corrosion
The direct chemical action of atmospheric gases (like oxygen, halogen, H2S etc.) in a dry
environment on metals, a solid film of the corrosion produced is formed on the surface of the
metal. This is known as chemical corrosion.
There are 3 main types of chemical corrosion.
1) Corrosion by oxygen (or) oxidation corrosion.
2) Corrosion by other gases like SO2, CO2, H2S and F2 etc.
3) Liquid metal corrosion.
1. Oxidation corrosion (Reaction with oxygen): Some of the metals directly react with oxygen in
the absence of moisture. Alkali and alkaline earth metals react with oxygen at room temperature
and form corresponding oxides, while some metals react with oxygen at higher temperature.
Metals like Ag, Au and Pt are not oxidized as they are noble metals. During oxidation of a metal,
metal oxide is formed as a thin film on the metallic surface which protects the metal from further
corrosion. If diffusion of either oxygen or metal is across this layer, further corrosion is possible.
Thus, the layer of metal oxide plays an important role in the process of corrosion. If the metal
oxide film is

a. Stable layer: A stable layer is fine grained in structure and can get adhered tightly to the parent
metal surface. Such a layer will be impervious in nature and hence behaves as protective coating,
thereby shielding the metal surface. Consequently further oxidation corrosion is prevented.

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E.g.: Al, Cr, W, Sn, Ti, Pb, Cu, etc. from stable oxide layers on surface thus preventing further
oxidation.
b. Unstable Layer: The oxide layer formed decomposes back into metal and oxygen.
Consequently, oxidation corrosion is not possible in such cases.
Eg: Ag, Au and Pt do not undergo oxidation corrosion.
c. Volatile Layer: The oxide layer formed is volatile in nature and evaporates as soon as it is
formed. There by leaving the under lying metal surface exposed for further attack. This causes
rapid continuous corrosion, leading to excessive corrosion.
eg: molybdenum (Mo) forms volatile MoO3 layer.
d. Porous Layer: Contains pores and cracks. In such a case the atmospheric oxygen has access to
the underlying surface of the metal through the pores or cracks of the layer, there by corrosion
continuous until the entire metal is converted to its oxide.
eg: alkali and alkaline earth metals (like Li, K, Na, Mg) form porous oxide layers.

2. Corrosion by other gases such as Cl2, SO2, H2S, NOx: In dry atmosphere, these gases react
with metal and form corrosion products which may be protective or non-protective. Dry Cl2 reacts
with Ag and forms AgCl which is a protective layer, while SnCl4 is volatile. In petroleum industries
at high temperatures, H2S attacks steel forming FeS scale which is porous and interferes with
normal operations.
3. Liquid metal corrosion: It is due to chemical action of flowing liquid metal at high temperatures
on solid metal or alloy. Such corrosion occurs in nuclear power devices. The corrosion reaction
involves either.
a) Dissolution of a solid metal by a liquid metal (or)
b) Internal penetration of the liquid metal into the solid metal.
Both these types of corrosion cause weakening of the solid metal.
For eg. in nuclear reactors liquid sodium corrodes Cd rods.

Pilling-Bedworth rule: According to it “an oxide is protective or non-porous, if the volume of the
oxide is atleast as great as the volume of the metal from which it is formed”. On the other hand,
“if the volume of the oxide is less than the volume of metal, the oxide layer is porous (or non-
continuous) and hence, non-protective, because it cannot prevent the access of oxygen to the fresh
metal surface below”. Thus, alkali and alkaline earth metals (like Li, K, Na, Mg) form oxides of
volume less than the volume of metals. Consequently, the oxide layer faces stress and strains,
thereby developing cracks and pores in its structure. Porous oxide scale permits free access of
oxygen to the underlying metal surface (through cracks and pores) for fresh action and thus,
corrosion continues non-stop. Metals like aluminum forms oxide, whose volume is greater than
the volume of metal. Consequently, an extremely tightly-adhering non-porous layer is formed.
Due to the absence of any pores or cracks in the oxide film, the rate of oxidation rapidly decreases
to zero.

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Wet (or) electrochemical corrosion:
This type of corrosion is observed when a conducting liquid is in contact with a metal (or) when
two dissimilar metals are either immersed or dipped partially in a solution.
The corrosion occurs due to the existence of separate anodic and cathodic areas or parts between
which current flows through the conduction solution.
In the anodic area, oxidation reaction takes place so anodic metal is destroyed by dissolving (or)
forming a compound such as an oxide. Hence corrosion always occurs at anodic areas.

In cathodic area, reduction reaction (gain of electrons) takes place. So at cathodic part dissolved
constituents in the conducting medium accept the electrons either by: a) evolution of hydrogen or
b) absorption of oxygen depending on the nature of the corrosive environment.

Mechanism of wet or electrochemical corrosion:

a) Evolution of hydrogen:
This type of corrosion occurs usually in acidic environments. The corrosion of iron takes place in
acidic environment in the following way.
At anode the dissolution (oxidation) of iron to
ferrous ion with liberation of electrons takes place.

These electrons flow through the metal from anode

to cathode (acidic region) where H+ ions are
eliminated as H2 gas.

The overall reaction is

In this case, metals react in the acidic environment and are dissolved (undergo corrosion) to release
H2 gas. All metals above hydrogen in electrochemical series can show this type of corrosion. In
hydrogen evolution type of corrosion, anodic area is large as compared to its cathodic area.

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b. Absorption of oxygen:

Rusting of iron in neutral aqueous solution of

electrolytes like NaCl in the presence of
atmospheric oxygen is a common example of this
type of corrosion.
The surface of iron will be usually coated with a
thin film of iron oxide. However if this oxide film
develops some cracks, anodic areas are created
on the surface. While pure metal parts act as
cathode. Thus anodic areas are very small surface
parts. The rest of the surface of the metal forms
cathodes. Thus at the anodic part iron metal
dissolves as Fe+2 ions with the liberation of
electrons.

The liberated electrons flow from anodic to cathodic areas through iron metal during which they
interact with dissolved oxygen and moisture.

The Fe+2 ions and OH ̶ ions diffuse and form ferrous hydroxide precipitate when they meet with
each other.

If enough oxygen is present Fe(OH)2 is easily oxidized to Fe(OH)3 (ferric hydroxide).

The product, called yellow rust, actually corresponds to Fe2O3.H2O.

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Difference between dry and wet corrosion:

S.No. Dry corrosion Wet corrosion

1 Corrosion occurs in the absence of Corrosion occurs in presence of conducting
moisture. medium.
2 It involves direct attack of chemicals It involves formation of electrochemical cells.
on the metal surface.
3 Corrosion products are produced at the Corrosion occurs at anode but rust is
site of corrosion. deposited at somewhere between anode and
cathode.
4 The process of corrosion is uniform. It depends on the size of the anodic and
cathodic parts of metal.
5 The process is slow. It is a rapid process.

Galvanic corrosion:
When two dissimilar metals are electrically connected and exposed to an electrolyte, the metal
higher in electrochemical series undergoes corrosion. This type of corrosion, is called galvanic
corrosion (or bimetallic corrosion). In this process, the more active metal (with more negative
electrode potential) acts as an anode while the less active metal (with less negative electrode
potential) acts as a cathode.
Zinc and copper metals connected with each
other in an electrolyte medium form a galvanic
cell. Zinc acts as anode and undergoes
corrosion while cathode (Cu) will be
unaffected.
Mechanism: In acidic solution, the corrosion
occurs by the hydrogen evolution process; while in neutral or slightly alkaline solution, oxygen
absorption occurs. The electron-current flows from the anode metal, zinc to the cathode metal,
copper.

Thus it is evident that the corrosion occurs at the anode metal; while the cathodic part is protected
from the attack.

Passivity: It is displayed by some metals as Al, Cr, W, Ti, Ni etc. The passive behavior of these
metals is resulted from the formation of highly adherent and very thin oxide film on the metal
surface. This film acts as a protective barrier to further corrosion.

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Galvanic series: It is the series of metals and alloys that is made keeping in view the process of
corrosion of a metal or alloy in a particular atmosphere, i.e. sea water. Based on this, a galvanic or
activity series can be drawn up as shown below,

Factors influencing corrosion:

The rate and extent of corrosion depend mainly on

(a) The nature of the metal and (b) nature of the environment.

a. Nature of the Metal

1. Position of the metals in galvanic series: The extent of corrosion depends upon the position
of the metal in the galvanic series. Greater the oxidation potential, the greater is the rate of
corrosion. When two metals are in electrical contact, the metal higher up in the galvanic series
becomes anodic and suffers corrosion. Further, the rate and severity of corrosion depend upon
the difference in their positions in the galvanic series. The greater is the difference, the faster
is the corrosion of anodic metal.
2. Relative areas of the anode and cathode: 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 anodic part.
The rate of corrosion is more when the area of the cathode is larger. When the cathodic area is
larger, the demand for electrons will be more, and this results in increased rate of dissolution
of metals at anodic regions.
3. Purity of metal: Pure metal resists corrosion, while impurities in a metal form a local galvanic
cell (metal as anode and impurity as cathode) and result in the corrosion of metal. Rate of
corrosion increases due to more exposure of impurities.
4. Nature of corrosion product-solubility: Solubility of the corrosion product formed is an
important factor in corrosion. If the corrosion product is soluble in the corroding medium, the
corrosion of the metal will proceed faster. On the other hand, if the corrosion product is
insoluble, then the protective film formed tends to suppress corrosion.

5. Nature of the corrosion product-volatility: If the corrosion product is volatile, it volatilizes as

soon as it is formed, thereby leaving the underlying metal surface exposed for further attack.
This causes rapid and continuous corrosion, leading to excessive corrosion. For example,
molybdenum oxide (MoO3) the oxidation corrosion product of molybdenum, is volatile.

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b. Nature of the Environment

1. Temperature: The rate of chemical reactions and the rate of diffusion of ions increase with
temperature. Hence, corrosion increases with temperature.

2. Humidity: Humidity and time-of-wetness play a large role in promoting and accelerating
corrosion rates. For example, atmospheric corrosion of iron is slow in dry air but increases
rapidly in the presence of moisture. This is due to the fact that moisture acts as the solvent for
the oxygen in the air to furnish the electrolyte essential for setting up a corrosion cell. Rusting
of iron increases when the relative humidity of air reaches from 60 to 80%.
In humidity, gases like CO2, SO2, NOx are dissolved which form electrolytes. It will cause
galvanic corrosion. Some oxides are water soluble, humidity washes away the corrosion
products and metal surface is further corroded. Other soluble corrosion products can also be
washed away by humidity, causing further corrosion.
3. Effect of pH:
In acidic medium, corrosion is faster the rate of corrosion is more compared to alkaline and
neutral medium.
Example:
If the pH is 3 or lower than 3 severe corrosion occurs in the absence of air due to the continuous
evolution of H2 at cathode. If the pH is greater than 10, corrosion of iron is very less due to the
formation of protective coating of hydrous oxides of iron.

{However, in basic medium pH > 7, some metals such as Pb, Zn, Al, etc. form complexes and
hence they corrode.
Example: Zn corrodes minimum at pH 11, but at higher pH (more than 11) it corrodes faster.}

Corrosion control methods

1. Cathodic protection:

It is a technique used to control the corrosion of a metal surface by making it the cathode of an
electrochemical cell. Since there will not be any anodic area on the metal, corrosion does not occur.

There are two methods of applying cathodic protection to metallic structures.

a) Sacrificial anodic protection (galvanic protection)

b) Impressed current cathodic protection

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a) Sacrificial anodic protection method

In this method, the base metal to be protected

from corrosion is made cathode by connection it
with more active metal (anodic metal). Hence,
all the corrosion will concentrate only on the
active metal. The parent structure is thus
protected. The more active metal so employed is
called sacrificial anode. The corroded sacrificial
anode block is replaced by a fresh one. Metals
commonly employed as sacrificial anodes are
Mg, Zn, Al and their alloys. Magnesium has the
most negative potential and can provide highest
current output and hence is widely used in high
resistivity electrolytes like soil.

Applications:
1. Protection of buried pipelines, underground cables from soil corrosion.
2. Protection of pipes, cables and ship hulls from marine corrosion.
3. Insertion of magnesium sheets into the domestic water boilers to prevent the formation of rust.
4. Calcium metal is employed to minimize engine corrosion.

b) Impressed current cathodic protection:

In this method, an impressed current is applied in opposite direction to nullify the corrosion
current. This is done to convert the corroding metal from anode to cathode. Thus the metal
becomes cathodic and it is protected
from corrosion. The impressed current is
taken from a battery or rectified on A.C.
line. The anode is usually insoluble
electrode like graphite or platinum. The
insoluble electrode is buried in a back
fill of coke or gypsum to increase the
electrical contact with surrounding soil.
Applications: This type of impressed
current cathodic protection is given to 1)
Marine pipes or cables, 2) Water tanks
and 3) Buried water or oil pipelines.

2. Metallic Coating:

Deposition of protective metal over the surface of base metal (metal to be protected from
corrosion) is known as metallic coatings.
The surface of the base metal is coated with another metal (coating metal). Metallic coatings
are broadly classified into anodic and cathodic coatings.

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a. Anodic coating:

In this method, the metal used for the surface coating is more anodic than the base metal which
is to be protected. For example, coating of Al, Cd and Zn on steel surface are anodic because
their electrode potentials are lower than that of the base metal iron. Therefore, anodic coatings
protect the underlying base metal sacrificially.
The formation of pores and cracks over the metallic coating exposes the base metal and a galvanic
cell is formed between the base metal and coating metal. The coating metal dissolves anodically and
the base metal is protected.

NOTE: Galvanizing is a process in which the iron article is protected from corrosion by coating
it with a thin layer of zinc.

b. Cathodic coating:

Cathodic coatings are obtained by coating a more noble metal (Sn, Au, Ag, Pt etc.) than the base
metal. They protect the base metal as they have higher corrosion resistance than the base metal due
to cathodic nature. Cathodic coating protects the base metal only when the coating is uniform and
free from pores. The formation of pores over the cathodic coating exposes the base metal (anode)
to environment and a galvanic cell is set up. This causes more damage to the base metal.

NOTE: The process of coating tin over the iron articles to protect them from undergoing corrosion
is known as tinning.

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Electroplating or Electro-deposition
It is the deposition of metal on the base metal by passing direct current through an electrolytic
solution of a soluble salt of the coat metal. The base metal to be electroplated acts as cathode.

Electroless Plating

Electroless plating is a technique of depositing a noble metal (from its salt solution) on a
catalytically active surface of the metal to be protected by using a suitable reducing agent
without using electrical energy.

The reducing agent reduces the metal ions. The metal atoms get deposited over the surface to
give a thin uniform coating.

Electroless nickel plating

The various steps are:

Step I : Pretreatment and activation of the surface:
The surface to be plated is degreased by using organic solvents and then accompanied by acid
treatment.
i) The surface of stainless steel is activated by dipping in hot solution of 50% H2SO4.
ii) Al, Cu, Fe, brass etc, do not require activation.
iii) Plastic, glass etc, are activated by dipping in a solution of SnCl2 and then in PdCl2 solution.
On drying a thin layer of palladium is formed on the surface.
Step II : Preparation of plating bath:
The plating bath consists of:
i) Coating Metal: A solution of NiCl2 (20g/L)
ii) Reducing agent: Sodium hypophosphite (20g/L)
iii) Complexing agent: Sodium succinate (15g/L)
iv) Buffer to maintain pH at 4.5: Sodium acetate (10g/L)
v) Temperature: 93oC.

Step III: Procedure

The pretreated object is immersed in the plating bath for required time. The following reactions
occur and nickel is coated on the object.

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Uses of Nickel Plating
i) For decorative coating of jewellery, decorative items and automobile spares
ii) For coating of polymers for decorative purpose.
iii) For electronic appliances.

Advantages of electroless plating over electro plating

i) Electricity is not necessary
ii) Complicated parts are uniformly coated
iii) Plastics, glass etc, are easily coated
iv) Good mechanical, chemical and magnetic properties are obtained.

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