Module 3: Corrosion and Electrode System

Q1. Define metallic corrosion. Describe the electrochemical theory of corrosion

taking iron as an example.

Metallic Corrosion
Metallic corrosion is the gradual degradation of metals due to chemical or electrochemical
reactions with their environment.
Example: Rusting of iron
Electrochemical Theory of Corrosion
The electrochemical theory of corrosion explains corrosion as a redox reaction occurring in
the presence of moisture and oxygen. It involves the formation of anodic and cathodic
regions on the metal surface.
Mechanism of Iron Corrosion:
Formation of Anodic and Cathodic Sites:
o Due to surface impurities, iron (Fe) develops anodic and cathodic regions in
the presence of an electrolyte (e.g., water with dissolved oxygen).
Anodic Reaction (Oxidation):
o At the anode, iron loses electrons and forms iron ions: Fe → Fe2+ + 2 e-
o This reaction leads to the dissolution of iron.
Cathodic Reaction (Reduction):
o The electrons lost by iron are accepted by oxygen and water at the cathodic
region: O2 + 4H+ + 4e- → 2H2O
o In neutral or slightly basic conditions, the reaction is:
O2 + 2 H2O + 4e− → 4 OH−

Formation of Rust (Hydrated Iron Oxide):

o The Fe²⁺ ions react with OH⁻ to form iron(II) hydroxide:
2 Fe2+ + 4 OH− → 2 Fe(OH)2
o Further oxidation of Fe(OH)₂ in air leads to rust [hydrated iron(III) oxide]:
4 Fe(OH)2 + O2 + 2H2O→ 2 [Fe2O3.3H2O] Yellow rust
o In the presence of oxygen, ferrous hydroxide is converted into magnetic oxide,
known as black rust.
3 Fe(OH)2 + ½ O2 → Fe3O4.3H2O Black rust
Q2. Discuss the following types of Corrosion:
a. Differential metal corrosion b. Differential aeration corrosion

a) Differential Metal Corrosion (Galvanic Corrosion)

This type of corrosion occurs when two dissimilar metals are in electrical contact in the
presence of an electrolyte (such as water or moisture). The metal with a lower electrode
potential (anode) corrodes faster, while the other (cathode) is protected.
Example:
• When iron and copper are in contact in seawater, iron corrodes faster, while copper
remains unaffected.
Cell reactions:
At anode: Fe → Fe2+ + 2e-
At cathode: O2 + 2 H2O + 4e- → 4 OH-
Fe2+ + 2 OH- → 2 Fe(OH)2
4Fe(OH)2 + O2 + 2H2O→ 2 [Fe2O3.3H2O]

b) Differential Aeration Corrosion

This occurs due to variations in oxygen concentration in different parts of a metal surface
exposed to an electrolyte. The region with less oxygen concentration (anode) corrodes faster,
while the area with more oxygen concentration (cathode) remains protected.

Example:
• Pitting Corrosion &
waterline corrosion: In
water tanks, stagnant
water areas have lower
oxygen, causing
localized corrosion (pits).

Q3. What is differential aeration corrosion? Explain pitting and waterline

corrosion with suitable reactions.
Differential aeration corrosion or oxygen differential cell corrosion, occurs when there are
variations in the concentration of oxygen within an electrolyte in contact with a metal surface.
Water line corrosion
❖ Waterline corrosion occurs on metal structures at the waterline, where the surface is
exposed to both air and water.
❖ The portion above the waterline is exposed to high oxygen concentration, acts as a
cathodic area, and remains unaffected.
 ❖ While the portion below the waterline has a low oxygen concentration acts as an anodic
area that undergoes corrosion.
❖ A distinct brown line is formed just below the water line due to the deposition of rust.
Cell Reaction:
At anode: Fe → Fe2+ + 2e-
At cathode: O2 + 2 H2O + 4e- → 4 OH-
2 Fe2+ + 4 OH- → 2 Fe(OH)2
4 Fe(OH)2 + O2 + 2H2O→ 2 [Fe2O3.3H2O]

Pitting line corrosion

❖ Pitting line corrosion arises when a small portion of the metallic surface is covered
by dust or oil drops.
❖ The metal portion below the dust which is exposed to a low oxygen concentration
acts as an anodic area that undergoes corrosion and a pit is formed.
❖ The whole remaining part of the metal which is exposed to a high oxygen
concentration acts as a cathodic area and remains unaffected.

Cell Reaction:
Similar cell reactions like waterline corrosion

Q4. Define galvanization. Describe the galvanization of iron and mention its
applications.
Galvanization is the process of coating iron or steel with a protective layer of zinc to prevent
rusting. The zinc coating acts as a barrier and provides sacrificial protection when exposed to
moisture and air.
Hot-dip galvanization involves the following steps:

• Surface Cleaning – The iron object is cleaned using acid (pickling) or alkali
solutions to remove rust, dirt, and grease.
• Fluxing – The cleaned iron is treated with a zinc ammonium chloride solution to
prevent oxidation before dipping.
• Dipping in Molten Zinc – The iron is immersed in molten zinc at around 450°C,
forming a strong metallurgical bond with the surface.
• Cooling & Solidification – The coated iron is removed and cooled, allowing the
zinc layer to solidify.
• Removal of excess zinc – Excess zinc is released by passing the metal through
rollers (or) by wiping.
 • Inspection–The final product is checked for uniform coating and durability.

Applications of Galvanized Iron

• Construction
• Automobile Industry
• Household Items
• Electrical Equipment
• Water Pipes

Q5. What is the anodizing process? Describe the anodizing of aluminium and
mention its applications.

Anodizing is the process of oxidation of the outer layer of metal to its metal oxide by
electrolysis. The metal oxide layer formed through anodization serves as a protective barrier
between the metal substrate and the surrounding environment.

Cleaning: The aluminum surface is cleaned with alkaline or acidic solutions to remove dirt,
grease, and oxides.
Electrolytic Bath: The aluminum workpiece is placed in an electrolyte solution (usually
chromic acid) and connected to the anode in an electrolytic cell.
Electrolysis: When current is passed through the electrolyte, oxygen is released at the
aluminum surface, reacting with the metal to form a thick aluminum oxide (Al₂O₃) layer.
Sealing: The porous oxide layer is sealed by
immersing the anodized aluminum in hot water to
close the pores, improving corrosion resistance.

Cell Reaction
Anode reaction: 2Al + 3H2O → Al2O3 + 6H+ +6e-
Cathode reaction: 6H+ + 6e- → 3H2
Overall: 2Al +3H2O → Al2O3 + 3H2
Applications:
• Aerospace Industry: Used in aircraft components
• Automobile Industry: Used in car parts
• Electronics: in smartphone casings
• Architectural Applications: Used in window frames, doors
• Kitchenware

Q6. What is cathodic protection? Describe the sacrificial anode technique and
mention the advantages and disadvantages.

Cathodic protection
Cathodic protection is a method of protecting a metal structures from corrosion by converting
it completely into cathode of an electrochemical cell where another metal (the anode)
corrodes instead.
Sacrificial Anodic Protection
Sacrificial anodic protection is a corrosion prevention method where a more reactive metal
(such as zinc, magnesium, or aluminum) is attached to a metal structure, like pipelines or
ships. This reactive metal acts as the anode and corrodes instead of the protected metal (the
cathode). As the sacrificial anode oxidizes, it releases electrons, preventing the cathode from
corroding. This method is widely used in marine and underground applications but requires
periodic replacement of the anodes.
Advantages
• Simple installation and maintenance
• No external power source required
Disadvantages
• Limited lifespan; anodes need
replacement
• Not effective for large structures without multiple anodes
• Can become costly over time due to frequent replacements

Q7. Define CPR.

Corrosion Penetration Rate (CPR)
The speed at which any metal in a specific environment deteriorates due to a chemical
reaction in the metal when it is exposed to a corrosive environment.
The CPR is calculated as follows:
CPR = (K x W) / (D x A x T)
Where, K = a constant (constant depends on the unit used.
when K = 534, the mpy will be used. when K = 87.6,
mm/yr will be used.
W = total weight lost
T = time taken for the loss of metal
A = the surface area of the exposed metal
D = the metal density in g/cm³
[1 inch2 = 6.45 cm2]

Numerical on Corrosion penetration rate (CPR)

Q8. Define corrosion. Mention at least six implications of corrosion.

Metallic Corrosion
Metallic corrosion is the gradual degradation of metals due to chemical or electrochemical
reactions with their environment.
Example: Rusting of iron

Implications of Corrosion:

• Structural Damage: Corrosion weakens buildings, bridges, pipelines, and

machinery, leading to potential failures and collapses.
• Economic Loss: Huge financial resources are spent on repairing, replacing, and
maintaining corroded equipment and infrastructure.
• Safety Hazards: Corroded gas pipes, fuel tanks, and industrial machinery increase
the risk of explosions, leaks, and accidents.
 • Reduced Efficiency: Corrosion affects the performance of engines, turbines, and
electrical systems by increasing resistance and reducing energy efficiency.
• Contamination of Products: In industries like food, pharmaceuticals, and water
supply, corrosion can contaminate products, making them unsafe for consumption.
• Environmental Damage: Corrosion of ships, oil rigs, and pipelines can lead to oil
spills and chemical leaks, harming marine life and ecosystems.

Q9. Explain the different types of electrodes with suitable examples.

1. Metal-Metal ion electrode: An electrode of this type consists of a metal dipped in a

solution containing its ions.
Example: Zn/Zn²+, Cu/Cu²+ etc

2. Metal-Metal salt ion electrode: These electrodes consist of a metal which is in contact
with a sparingly soluble salt of the same metal dipped in a solution containing an anion
of the salt.
Example: Calomel (Hg/Hg₂Cl₂|CI-), Silver-Silver salt electrode (Ag/ AgCI / CI-)

3. Gas electrode: Gas electrode consists of a gas bubbling about an inert metal wire,
immersed in a solution containing ions to which the gas is reversible.
Example: Hydrogen electrode: Pt/H2(g) 1 atm /H+ (1M)

4. Oxidation-Reduction electrode: An oxidation-reduction electrode is a one in which

the electrode potential arises from the presence of oxidized and reduced forms of the
same substance in solution. The potential developed is picked up by an inert electrode
like platinum.
Example: Pt|Fe²+, Fe³+ and Pt/Sn2+, Sn3+

5. Ion-selective electrode: The ion-selective electrode generally consists of a membrane

that selectively responds to a specific ion in a mixture of ions in solutions that ignore all
other ions and develop a potential.
Example: Glass electrode.
Q10. Define Ion selective electrode. Explain the construction and working of ion
selective electrode.
Ion selective electrode:
The ion-selective electrode generally consists of a membrane that selectively responds to
a specific ion in a mixture of ions in solutions that ignore all other ions and develop a
potential.
Example: Glass electrode.
Cell construction of glass electrode
• The glass electrode consists of a glass tube made up of a special type of glass with
high electrical conductivity.
• The glass tube contains a solution of concentration C1 (0.1M HCl)
• An Ag-AgCl electrode is placed inside the solution which acts as an internal
reference electrode and also serves for the external electrical contact.
• The glass electrode is dipped in unknown solution of concentration C2.
Cell representation
Ag / AgCl /HCl (0.1M) / unknown solution / Glass

Working
• The potential developed across
the membrane by the exchange
of ions is known as boundary
potential Eb = E2– E1. E2 and E1
are the potentials developed at
the outer and inner membrane
respectively.
• Even when C1=C2, E ≠ 0, a small
potential is developed across the membrane; this is called an asymmetric
potential (Easy).

Therefore, the boundary potential

Eb = E2 - E1
0.0591 0.0591
= (E° + log C2) - (E° + log C1)
𝑛 𝑛
0.0591 0.0591
= log C2 - log C1
𝑛 𝑛
0.0591 0.0591 1
= log C2 + log
𝑛 𝑛 𝐶1
0.0591 0.0591 1
= log C2 + L Where L = log
𝑛 𝑛 𝐶1
Here n=1, [C2] = [H+] ions in outer membrane, Then 𝐸𝑏 = L + 0.0591 log [H+]
Eb = L - 0.0591 pH Where pH= - log [H+]
The Glass electrode potential is given by EGlass = Eb + Easy+ EAg/AgCl
Substitute the value of Eb
𝐸𝐺 = L - 0.0591 pH + Easy+ EAg/AgCl
Consider L1 = L + Easy+ EAg/AgCl,
Therefore, EG = L1− 0.0591 pH

Q11. Define Ion selective electrode. Explain how a glass electrode can be used to
determine the pH of an unknown solution.
Ion selective electrode:
The ion-selective electrode generally consists of a membrane that selectively responds to
a specific ion in a mixture of ions in solutions that ignore all other ions and develop a
potential.
Example: Glass electrode.

We know that the electrode potential of

the glass electrode depends on the
concentration of H+ ions.
EG = L1− 0.0591 pH
where pH = -log [H+] and L1 is a constant

To determine the pH of an unknown

solution the cell assembly will be
a calomel electrode and Glass electrode. Where the Calomel Electrode is used as the
reference electrode It has stable known electrode potential.
The calomel electrode and the glass electrode are both immersed in the unknown
solution, forming an electrochemical cell.

The cell assembly is represented as:

Hg/Hg2Cl2/Cl- // solution of unknown pH / glass /0.1 M HCl / AgCl / Ag

The overall potential of this cell (Ecell) is the difference between the glass electrode
potential EG and the calomel electrode potential Ecal.
Ecell = ECathode - EAnode
= EG - ECal
= L1− 0.0591 pH - ECal
𝐊−𝐄𝐜𝐞𝐥𝐥
pH = Where K is electrode assembly constant, K = L1-Ecal
𝟎.𝟎𝟓𝟗𝟏
From this equation, by measuring the potential difference between the calomel reference
electrode and the pH-sensitive glass electrode, we can determine the pH of the unknown
solution.

Q12. What are reference electrodes? Explain the construction, working and
application of Calomel electrode.
Reference Electrode:
A reference electrode is an electrode that has a stable and well-known electrode
potential. This electrode is used to determine the electrode potential of other electrodes.
Construction of Calomel electrode
• The calomel electrode consists of two glass tube.
• At the inside glass tube, there is a paste (calomel) of
mercury and mercurous chloride (Hg2Cl2) at the
bottom of a narrow glass tube.
• Pure mercury is filled below the paste and
connected with platinum wire for external electrical
contact
• This narrow tube placed inside an outer glass tube
filled with a saturated KCl solution.
Cell representation
The calomel electrode is represented as, Hg/ Hg2Cl2 / KCl

Working
Calomel electrode can behave as an anode or cathode depending upon the nature of
another electrode.
When it acts as an anode, oxidation takes place. Thus, the half-cell reaction is
2𝐻𝑔 + 2𝐶𝑙− → 𝐻𝑔2𝐶𝑙2 + 2𝑒−
When it acts as a cathode, reduction takes place. Thus, the half-cell reaction is
𝐻𝑔2𝐶𝑙2 + 2𝑒− →2𝐻𝑔 + 2𝐶𝑙−
The net cell reaction is, 𝐻𝑔2𝐶𝑙2 + 2𝑒− ↔ 2𝐻𝑔 + 2𝐶𝑙−
The electrode potential for the calomel electrode is
0.0591 1
E = E° + log
2 [Cl−]2

E = E° - 0.0591 log [Cl-] at 298K

• The calomel electrode potential is depending on the concentration of chloride ions

in KCl.
Applications
1. It is used as a secondary reference electrode to measure single electrode potentials.
2. It is used in potentiometric analysis.

Q13. What is concentration cell? Explain the construction and working of

concentration cells.

The concentration cells consist of identical electrodes immersed in the solutions of the
same electrolytes but with varying concentrations. The potential difference arises due to
differences in electrolyte concentration.

Construction
There are three components
• Electrodes: The two electrodes are
called the cathode (right side) and
the anode (left side). The anode
loses electrons through an
oxidation reaction. The cathode
gains electrons through a
reduction reaction.
• Salt Bridge: A salt bridge connects the two compartments (anode & cathode) to
maintain charge balance. It consists of a saturated solution of a salt such as KCl.
• Voltmeter: The voltmeter is used to measure the cell potential of the cell.

Cell representation: Concentration cell is represented as,

Cu/Cu+2 (C1= 0.01M) || (C2= 0.1M) Cu+2/Cu

Working
Anode: Cu Cu+2 (C1) +2e-
Cathode: Cu+2 (C2) +2e- Cu
Net cell reaction: Cu (C2)
+2 Cu+2 (C1)

The electrode potential for the concentration cell is represented by

Ecell = ECathode - EAnode
0.0591 0.0591
=(E⁰Cathode + log C2) - (E⁰Anode + log C1)
𝑛 𝑛
In a concentration cell, both electrodes are same, hence
𝟎.𝟎𝟓𝟗𝟏 𝐂𝟐
Ecell = log at 298K
𝒏 𝐂𝟏
Now, Ecell will be positive only if C2 > C1.
Numerical on Concentration Cell

A concentration cell is constructed by dipping copper rods in 0.001M and 0.1 M

copper sulphate solutions. Calculate the EMF of the cell at 298K.
Cell representation:
Cu/Cu+2 (C1= 0.001M) || (C2= 0.1M) Cu+2/Cu
Cell reactions:
Anode: Cu Cu+2 (C1) +2e-
Cathode: Cu+2 (C2) +2e- Cu
Net cell reaction: Cu (C2 = 0.1M)
+2 Cu+2 (C1 = 0.001M)
0.0591 C2
Now, Ecell = log at 298K
𝑛 C1
0.0591 0.1
= log
2 0.001
= 0.0591 V
EMF of the cell Cu/CuSO4 // CuSO4/Cu is 0.0595V at 25°C. C1= 0.001M, C2 = X and n=
2. Find X value?

Cell representation:
Cu/Cu+2 (C1= 0.001M) || (C2= x M) Cu+2/Cu
Cell reactions:
Anode: Cu Cu+2 (C1) +2e-
Cathode: Cu+2 (C2) +2e- Cu
Net cell reaction: Cu+2 (C2 = x M) Cu+2 (C1 = 0.001M)
0.0591 C2
Now, Ecell = log at 298K
𝑛 C1
0.0591 x
0.0595 = log
𝑛 0.001
x = 0.103 M

EMF of the cell Ag/AgNO3 // AgNO3/Ag is 0.8V at 25°C. C2= 0.2M, Find C1 =?
Cell representation:
Ag/Ag+ (C1= x M) || (C2= 0.2) Ag+/Ag
Cell reactions:
Anode: Ag Ag+ (C1) +e-
Cathode: Ag+ (C2) +e- Ag
Net cell reaction: Ag+1 (C2 = 0.2M) Ag+ (C1 = x M)
0.0591 C2
Now, Ecell = log at 298K
𝑛 C1
0.0591 0.2
0.8 = log
1 C1
0.2 0.8
log =
C1 0.0591
 0.2
log = 13.536
C1
0.2
= Antilog (13.536) = 3.4355 x 1013
C1
C1 = 5.83 x 10-15 M

Q14. Briefly explain the principle, instrumentation and working of potentiometry

taking the estimation of Iron as an example.

Potentiometry: Principle:
Potentiometry is an electroanalytical technique used to determine an analyte's
concentration by measuring a solution's electrode potential. The potential is related to
the concentration of the analyte through the Nernst equation:
𝟎.𝟎𝟓𝟗𝟏
Ecell = E° + log [M+n]
𝒏

Instrumentation:
Indicator Electrode: A platinum electrode is used to determine electrode potential
due to Fe²⁺/Fe³⁺ concentration changes.
Reference Electrode: A Calomel Electrode (SCE) provides a stable reference
potential.
Potentiometer: Measures the potential difference between the indicator and reference
electrodes.
Titration Setup: A beaker containing Fe²⁺ solution with a buret for controlled
addition of the titrant (oxidizing agent like K₂Cr₂O₇).
Working:
• To determine the concentration of Fe²⁺ in a solution using a redox titration with
potassium dichromate (K₂Cr₂O₇) as the titrant. The sample solution contains Fe²⁺
ions in an acidic medium (H₂SO₄). Potassium dichromate (K₂Cr₂O₇) is used as the
titrant because it oxidizes Fe²⁺ to Fe³⁺. The Platinum and the calomel electrodes are
placed in the Fe²⁺ solution. The electrode potential is measured as K₂Cr₂O₇ is
gradually added.

Determination of End Point:

• As Fe²⁺ is oxidized to Fe³⁺, the potential of the solution changes. Near the equivalence
point, there is a sharp change in potential, which is recorded by plotting a
potentiometric titration curve (ΔE/ΔV vs. volume of titrant added). The volume
of K₂Cr₂O₇ at the equivalence point is used to calculate the concentration of Fe²⁺.
Q15. Explain the principle, instrumentation and working of conductometry taking
estimation of weak acid using a strong base as an example.

Principle:

Conductometry is based on the measurement of the electrical conductivity of an electrolyte

solution. Conductivity depends on the concentration, mobility, and charge of the ions present
in the solution. During a titration, the ionic composition changes, leading to variations in
conductivity, which can be used to determine the endpoint.

For estimation of a weak acid (e.g., acetic acid) using a strong base (e.g., NaOH),
the reaction follows:

CH3COOH + NaOH → CH3COO− + Na+ + H2O

Instrumentation:

• Conductivity cell – Consists of two platinum electrodes placed in the solution.

• Conductivity meter – Measures the conductance of the solution.
• Burette – Contains the titrant (NaOH).
• Beaker with sample solution – Contains the weak acid
• Magnetic stirrer – Ensures uniform mixing.

Working:

• A known volume of weak acid (CH₃COOH) is taken in a beaker, and the conductivity
cell is immersed in it. The conductivity of the initial solution is measured.
• A strong base (NaOH) is added from the burette in small increments while
continuously measuring conductivity.
• When NaOH is added to the acid, the salt formed is highly ionized and the
conductivity slightly increases. At the equivalence point, all acetic acid is
neutralized, and conductivity reaches a minimum.
• Beyond the equivalence point, excess NaOH increases conductivity due to the
presence of highly mobile OH⁻ ions.