Module 3: Corrosion and Electrode System
Q1. Define metallic corrosion. Describe the electrochemical theory of corrosion
taking iron as an example.
Corrosion: Corrosion is defined as the destruction and consequent loss of metals through
chemical or electrochemical attack by the environment
Example: Rusting of iron
Electrochemical theory of corrosion
❖ Corrosion involves the formation of an electrochemical cell between a metal
surface, an electrolyte, and the surrounding environment. This cell consists of an
anodic region and a cathodic region.
❖ At the anodic region oxidation reaction takes place and the metal gets corroded
into ions liberating the electrons. Consequently, metals undergo corrosion at the
anodic region.
❖ At the cathodic region reduction reaction takes place. Metal ions in the cathodic
region are unaffected by the cathodic reaction.
❖ The electrons liberated at the anodic region migrate towards the cathodic region
constituting a corrosion current.
❖ The metal ions liberated at the anode form a corrosion product between the anode
and the cathode.
Anodic Reaction (Oxidation process):
At the anodic area metal undergoes oxidation with the release of electrons
Fe → Fe2+ + 2 e-
Cathodic reaction (Reduction process)
❖ This reduction reaction consumes electrons and produces hydroxide ions The
general reduction reaction for oxygen can be represented as
O2 + 2 H2O + 4e- → 4 OH-
❖ Fe2+ ions combine with OH- ions near the cathodic area, forming insoluble
ferrous hydroxide.
2 Fe2+ + 4 OH- → 2 Fe(OH)2
❖ Ferrous hydroxide further combines with oxygen and water leading to the
formation of hydrated ferric oxide.
4 Fe(OH)2 + O2 + 2H2O→ 2 [Fe2O3.3H2O] Yellow rust
❖ 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
❖ Differential metal corrosion (bimetallic corrosion), occurs when two dissimilar
metals are in contact with each other in the presence of an electrolyte, such as
moisture.
❖ The metal with a lower reduction potential undergoes oxidation and acts as the
anode (the metal that corrodes) and the other metal with a higher reduction
potential undergoes reduction and acts as the cathode (the metal that is
protected).
❖ The higher the difference in electrode potential faster the rate of corrosion.
The standard electrode potentials of Fe and Cu are – 0.44 V and 0.34 V respectively. In
this case iron acts as an anode and undergoes corrosion whereas copper acts as the
cathode and remains unaffected.
Cell reactions:
During differential metal corrosion when Fe is in contact with Cu
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]
B. Differential aeration corrosion
❖ 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.
❖ The difference in oxygen concentration produces a potential difference and causes
corrosion current to flow from cathode to anode.
❖ Part of the metal exposed to a lower oxygen concentration will have lower
potential and therefore act as an anode. This part undergoes corrosion.
❖ The other part of the metal exposed to a higher oxygen concentration acts as a
cathode and remains unaffected.
Cell reactions:
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]
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. There are two types of differential aeration corrosion:
Water line corrosion
❖ Waterline corrosion occurs on metal structures at the waterline, where the
surface is exposed to both air and water.
❖ The waterline region experiences differential aeration conditions due to the
variation in oxygen concentration.
❖ 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.
❖ In the presence of a suitable corrosive environment metal is lost at that place
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:
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]
Q4. Define galvanization. Describe the galvanization of iron and mention its
applications.
Galvanization is a process used to coat steel or iron with a layer of zinc to protect the
underlying metal from corrosion. This process involves immersing the metal in a bath of
molten zinc or applying zinc coatings through hot-dip galvanizing.
The galvanization process involves the following steps.
• The metal surface is washed with organic solvents to remove organic impurities
such as oil and grease present on it.
• Then metal surface is washed with dilute sulphuric acid (pickling) to remove rust
and other inorganic deposits.
• Then it is washed well with water and air dried.
• The metal is treated with mixture of aqueous solution ZnCl2 and NH4Cl which acts
as flux and dried.
• The metal is then dipped in molten zinc maintained at 450°C.
• Excess zinc is released by passing the metal through rollers (or) by wiping.
Applications
Galvanized steel is used in
• infrastructure projects such as bridges, towers and light poles.
• the construction industry for a wide range of applications
• automotive manufacturing for components such as car bodies, frames
• various industrial applications for equipment and machinery components
• agricultural applications
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 aluminium substrate and the surrounding environment. This barrier
provides excellent corrosion resistance by preventing direct contact between the metal
surface and corrosive agents such as moisture.
During the anodization of aluminium, clean and polished aluminium is taken as an anode
and immersed in an acidic electrolytic solution of chromic acid and a direct current is
applied. An inert electrode like lead is generally used as a cathode. This causes an
oxidation reaction at the surface of the aluminium resulting in the formation of a thick
porous aluminium oxide layer. The pores are finally sealed by dipping in hot water to
produce Al2O3 .H2O, which acts as a non-porous protective layer preventing corrosion.
Cell Reaction
Anode reaction: 2Al + 3H2O → Al2O3 + 6H+ +6e-
Cathode reaction: 6H+ + 6e- → 3H2
Overall: 2Al +3H2O → Al2O3 + 3H2
Applications:
• Anodized aluminium is widely used in
various industries, including
aerospace, automotive, construction, and electronics, where corrosion
resistance and durability are essential requirements.
• Anodization is used for aluminium pressure cookers and cooking pots.
• Electronic casings, outdoor furniture, and window frames.
Q6. What is cathodic protection? Describe the sacrificial anode technique and
mention the advantages and disadvantages.
Cathodic protection is a method of protecting a metal from corrosion by converting it
completely into cathodic of an electrochemical cell and no part of it is allowed to act as
anode. This method is particularly effective for buried or submerged metal structures, such
as pipelines, and storage tanks.
Cathodic protection (Sacrificial anodic protection) relies on the principle of galvanic
corrosion, where a more reactive metal (anode) corrodes preferentially to a less reactive
metal (cathode) when they are electrically connected in an electrolyte.
• The base metal is usually iron, copper or brass.
• Metals like Mg, Al and Zn are more active and hence are used as anodes.
• Since the anodic metals are sacrificed to protect the metal structure, the method
is known as sacrificial anodic protection.
• These metals being more active act as anode undergo corrosion and supply
electrons to the target metal.
• In this way the protected metals act as cathode.
Advantages
• The method is simple.
• Low installation cost.
• Minimum maintenance cost.
• Does not require a power supply.
Disadvantages
• It requires regular monitoring and maintenance to ensure proper functioning
and effectiveness.
• complex to design, install, and maintain,
• Involves the consumption of metals such as zinc, aluminum, or magnesium,
which are released into the environment over time.
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
Q8. 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.
Q9. Define Ion selective electrode. Explain the construction and working of ion
selective electrode and how it can be used for the determination of pH of a 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.
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. Where 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, it is called as 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
Determination of pH using glass
electrode
The potential of a glass electrode depends
on the concentration of H+ ions. Hence, pH
of a solution can be determined by using a
glass electrode and calomel electrode
assembly.
The cell assembly is represented as:
Hg/Hg2Cl2/Cl- // solution of unknown pH / glass /0.1 M HCl / AgCl / Ag
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
Q10. 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.
• If the Concentration of chloride ions increases, the potential decreases and vice
versa. (The potential of calomel is inversely proportional to the concentration of
chloride ions)
Applications
1. It is used as a secondary reference electrode to measure single electrode potentials.
2. It is used in potentiometric analysis.
Q11. 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 is a device used in an electrochemical cell for connecting
its oxidation and reduction half cells. The main function of a salt bridge is to
maintain electrical neutrality within the internal circuit. It consists of a saturated
solution of a salt such as KCl or NH4NO3.
• 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+2 (C2) 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.
Q12. Briefly explain the principle, instrumentation and working of potentiometry
taking the estimation of Iron as an example.
Potentiometry; its application in the estimation of iron
Aim: Determination of the weight of ferrous ammonium sulphate and ferrous iron in the
given solution by potentiometric titration method.
Theory: In this titration, the amount of substance in the solution is determined by
measuring the emf between two electrodes that are dipped into the solution. When the
metal M is immersed in the solution containing its own ions Mn+ ions, the electrode
potential is given by the Nernst equation,
𝟎.𝟎𝟓𝟗𝟏
Ecell = E° + log [M+n]
𝒏
From this equation the potential of the electrode is directly proportional to the
concentration of the ionic species present in the solution.
Instrumentation:
A potentiometer consists of an indicator electrode (e.g.: Platinum) and a saturated
reference electrode (E.g.: Calomel electrode), stirrer & potentiometer to measure the
potential values.
EMF of the solution can be measured by combining the reference electrode with an
indicator electrode. The electrode which responds to the change in the concentration of
the ion in the solution is called indicator electrode & reference electrode is one whose
potential is constant. A known volume of the analyte is taken in beaker and its potential
is measured. The titrant is added in increments of 0.5 ml and potential is measured each
time. Near the equivalence point there is a sharp increase in the potential. The end point
is determined by plotting change in potential against volume of the titrant.
Applications
1. Estimation of the concentration of the ionic species present in the given solution.
2. Coloured solution can also be titrated
3. Acid-base titration can also be done in this method.
4. In this method Oxidation-reduction titrations can also be carried out.
5. Precipitation reactions can also be carried out potentiometrically.
For example:
Procedure: Pipette out 25 mL of FAS solution into a 50 mL beaker. Add one test tube full
of dilute H2SO4. Immerse Platinum. & calomel electrodes into the solution, & connect the
electrodes to a potentiometer. Fill the burette with K2Cr2O7 solution. Add K2Cr2O7
solution from the burette with an increment of 0.5 mL, stir well and measure the potential
after each addition. Continue the titration till the potential indicates a rapid jump with a
drop of the titrant. Plot the graph of ΔE/ ΔV v/s vol. of K2Cr2O7.
Q13. Explain the principle, instrumentation and working of conductometry taking
estimation of weak acid using a strong base as an example.
Conductometry; its application in the estimation of weak acid
Theory
Electrolyte solution conducts current by the migration of ions under the influence of an
electric field. This experiment is based on Ohm’s law which states that the current’ I ‘ flow
through conductor is directly proportional to the applied potential, E and inversely to the
resistance R of conductor.
E= I R
Specific conductance of an electrolyte solution is the conductance of the solution present
between two parallel electrodes of 1cm3 area of cross-section and 1cm apart.
Instrumentation
1. It consists of a platinum electrode each of unit area of cross-section placed unit
distance a part.
2. The electrodes are dipped in the electrolyte solution taken in a beaker.
3. It is connected to a conductivity meter.
4. The titrant (NaOH) is added from a burette and solution is stirred.
5. The conductance is measured after the addition of the titrant at intervals of 1.0 ml.
Application: Weak acid v/s Strong base (CH3COOH v/s NaOH)
Consider the titration of acetic acid against NaOH. The conductance of the acid will be
initially low since acetic acid is a weak electrolyte. When NaOH is added to the acid, the
salt formed is highly ionized and the conductance increases. On complete neutralization
of the acid, further addition of base leads to an increase in the number of mobile OH- ions.
Hence the conductance increases sharply.
CH3COOH+NaOH→CH3COONa+H2O
A plot of conductance against the volume of base added is shown in the figure. The point
of intersection of two curves gives the neutralization point.
