CMR INSTITUTE OF TECHNOLOGY

MODULE 3: Corrosion and Electrode System

Corrosion Chemistry: Introduction, electrochemical theory of corrosion, types of

corrosion-differential metal and differential aeration. Corrosion control -galvanization,
anodization and sacrificial anode method. Corrosion Penetration Rate (CPR) –
Introduction and numerical problem.
Electrode System: Introduction, types of electrodes. Ion selective electrode –
definition, construction, working and applications of glass electrode. Determination of
pH using glass electrode. Reference electrode -Introduction, calomel electrode –
construction, working and applications of calomel electrode. Concentration cell–
Definition, construction and Numerical problems.
Analytical Techniques: Introduction, principle and instrumentation of
Conductometry; its application in the estimation of weak acid. Potentiometry; its
application in the estimation of iron.

Corrosion
Corrosion is defined as the destruction and consequent loss of metals through chemical
or electrochemical attack by the environment

Example: Rusting of iron

Corrosion classified as
• Dry corrosion (Chemical corrosion)
Corrosion of metal occurs by direct attack of atmospheric gases such as oxygen in
the absence of moisture to form a metal oxide layer.
• Wet corrosion (Electrochemical corrosion)
Wet corrosion occurs in the presence of an aqueous solution of electrolyte and
atmospheric oxygen by setting up tiny galvanic cells on the metal surfaces.

Electrochemical theory of corrosion

• According to electrochemical theory, corrosion of the metal take place due to the
formation of anodic and cathodic regions on the same metal surface in the
presence of a conducting medium.
• 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.

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• The electrons liberated at the anodic region migrate towards the cathodic region
constituting corrosion current.
• The metal ions liberated at the anode form a corrosion product somewhere
between the anode and the cathode.
• Corrosion of metal continues as long as both the anodic and cathodic reactions
take place simultaneously.

Anodic Reaction (Oxidation process):

At the anodic area metal undergoes oxidation with the release of electrons
Fe → Fe2+ + 2 e-

Cathodic reaction (Reduction process)

The reaction at cathode (reduction reaction) depends on the nature of the environment:
If the medium is acidic,
(a) Liberation of Hydrogen: It takes place in the absence of oxygen
(i) In acidic medium
2 H+ + 2e-→ H2↑
(ii) Neutral / alkaline medium
2 H2O → 2 H+ + 2OH-
2 H+ + 2e- → H2
(b) Absorption of oxygen: It takes place in the presence of oxygen
(i) Acidic medium
O2 + 4 H+ + 4e- → 2 H2O
(ii) Alkaline medium

O2 + 2 H2O + 4e- → 4 OH-

Fe2+ ions combine with OH- ions near the cathodic area, forming insoluble ferrous
hydroxide.

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2 Fe2+ + 4 OH- → 2 Fe(OH)2

Ferrous hydroxide further combines with oxygen and water resulting 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

Types of Corrosion:
A. Differential metal corrosion
• When two dissimilar metals are in contact with each other, the metal with lower
reduction potential undergoes oxidation whereas the metal with higher
reduction potential undergoes reduction.
• The potential difference between the two metals is the cause for corrosion, higher
the difference faster is the rate of corrosion. The anodic metal undergoes corrosion
and the cathodic metal is unaffected.

Let us consider a bimetallic sample of iron and copper as shown below.

Case 1: The standard electrode potential of Fe is – 0.44 V which is less than that of Cu
whose standard electrode potential is 0.34 V. Hence in this case iron acts as anode and
undergoes corrosion whereas copper acts as cathode and remains unaffected.

Cell reactions:
During differential metal corrosion when Fe is in contact with Cu
At anode: Fe → Fe2+ + 2e-
At cathode: either hydrogen evolution or oxygen absorption
2 H+ + 2e- → H2↑
O2 + 2 H2O + 4e- → 4 OH-
B. Differential aeration corrosion
• It occurs when a metal surface is exposed to differential air (or) oxygen
concentration.

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• Part of the metal exposed to lower concentration of oxygen will have lower
potential and therefore acts as anode. This part undergoes corrosion.
• The other part of the metal exposed to higher concentration of oxygen acts as
cathode and remains unaffected.
• The difference in oxygen concentration produces a potential difference and causes
corrosion current to flow from cathode to anode.

B1. Water line corrosion

• This take place due to the formation of different oxygen concentration.

• The part of metal exposed to lower concentration of oxygen (dissolved oxygen)
acts as anodic area and undergoes corrosion.
• The part of the metal above the water level is exposed to higher concentration of
oxygen acts as cathodic are and remains unaffected.
• A distinct brown line is formed just below the water line due to the deposition of
rust.
• Water line corrosion is observed usually in steel water tanks and ships floating in
sea water for a long time.
Cell Reaction:
At the anode (less O2 concentration): Fe → Fe2+ + 2e-
At the cathode (more O2 concentration): O2 + 2 H2O + 4e- → 4 OH-
Fe2+ + 2OH- → Fe (OH)2
2Fe(OH)2+1/2O2+H2O → [Fe2O3. 3H2O] (rust)

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B2. Pitting line corrosion

• It arises when a small portion of the metallic surface is covered by dust or scale or
oil drops.
• The metal below the dust which is exposed to lower concentration of oxygen acts
as anodic area.
• In the presence of suitable corrosive environment metal is lost at that place a pit
is formed.
• The whole remaining part of the metal which is exposed to higher concentration
of oxygen acts as cathodic area and remains unaffected.
• Once a pit is formed corrosion occurs rapidly because of small anodic area (pit)
and large cathodic area.

Cell Reaction:
At the anode (less O2 concentration): Fe → Fe2+ + 2e-
At the cathode (more O2 concentration): O2 + 2 H2O + 4e- → 4 OH-
Fe2+ + 2OH- → Fe (OH)2

2Fe(OH)2+1/2O2+H2O → [Fe2O3. 3H2O] (rust)

Corrosion control
A. Metal coating: Galvanization
Galvanization is a process of coating a base metal surface with Zinc metal.
Galvanization consists of hot dipping method which involves the following steps.

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• 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.

B. Anodization
Anodizing is the process of oxidation of outer layer of metal to its metal oxide by
electrolysis. Metal oxide layer formed over the metal itself acts as protective layer.
In anodization of aluminium, clean and polished aluminium is taken as anode and
immersed in an electrolytic cell containing chromic acid. Inert electrode like lead is
generally used as cathode. The anodic oxide film formed on Al in bath as aluminium oxide,
which is porous. The pores are finally sealed by dipping in hot water to produce Al2O3
.H2O, which acts as a non-porous protective layer preventing corrosion.
Anode reaction: 2Al + 3H2O → Al2O3 + 6H+ +6e-
Cathode reaction: 6H+ + 6e- → 3H2
Advantages:
1. Anodized Al2O3 .H2O act as a protective layer, increasing the corrosion resistivity
of the surface as it prevents further oxidation.
2. They have harder and durability than normal aluminium.

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3. The anodized surface shows good adhesion to paint and gives a colored
appearance.

Applications:
• Anodization is used for aluminium pressure cookers and cooking pots.
• Aluminium window frames are anodized.
C. Cathodic protection
Cathodic protection is a method of protecting a metal or alloy from corrosion by
converting it completely into cathodic and no part of it is allowed to act as anode.
Example:

Sacrificial anodic protection:

• The base metal is usually iron, copper or brass.

• The metal to be protected from corrosion is converted into cathode by connecting
to a metal which is anodic to it.
• 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 anode method.
• These metals being more active acts as anode undergo corrosion and supply
electrons to the target metal.
• In this way the protected metals acts as cathode.

Advantages:
• The method is simple.
• Low installation cost.
• Minimum maintenance cost.
• Does not require power supply.
Applications:
a) A magnesium block connected to a buried oil storage tank.
b) Mg bars are fixed to the sides of ocean going ships to act as sacrificial anodes.
c) Mg blocks are connected to buried pipe lines.

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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 unit used. when K = 534, the mpy will be used.
when K = 87.6, mm/yr will be used.
W = total weight lost (mo – m) [m = weight after corroded mo = weight before corroded]
T = time taken for the loss of metal
A = the surface area of the exposed metal

D = the metal density in g/cm³

Numerical problems

1) A thick steel sheet of area 400 cm2 is exposed to air near the ocean. After 1 year it was
found to experience a weight loss 375 g due to corrosion. If the density of the brass is 7.9
g/cm3

2) A piece of corroded plate was found in the submerged ocean vessel. It was estimated
that the original area of the plate was 6.4 inch2 and that approximately 2.2 kg had
corroded away during the submersion for a period of 10 years. Calculate CPR in terms of
mpy and mm/y. Given density of iron = 7.9 g/cm3, K (mpy)= 534, K(mm/y)= 87.6.

Note:
Unit of CPR is mils per year (mpy) if W is in mg, A in Inch2, D in g/cm3, T in hrs and k value
will be 534.
Unit of CPR is mm/yr if W is in mg, A in cm2, D in g/cm3, t in hrs and K value will be 87.6.
Conversion factor: 1 inch2 = 6.45 cm2

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Electrode system
Electrode: An electrode is an electrical conductor used to make contact with a
nonmetallic part of a circuit.

Anode: Anode is an electrode where oxidation occurs.

Cathode: Cathode is an electrode where reduction process occurs.

Electrode potential: In electrochemistry, electrode potential is the electromotive force

of a galvanic cell built from a standard reference electrode and another electrode to be
characterized.

The electrode potential of an electrochemical cell is represented by

Ecell = Ecathode- Eanode

Nernst equation:
𝟐.𝟑𝟎𝟑𝑹𝑻
Ecell = E° + log [M+n]
𝒏𝑭
Substitute the value of R = 8.134 J K-1mol-1, T = 298 K and F= 96500 C/mol
𝟎.𝟎𝟓𝟗𝟏
Ecell = E° + log [M+n]
𝒏

Different types of electrodes

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+

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5. Ion selective electrode: In ion selective electrode, a membrane is in contact with a

solution, with which it can exchange ions.

Example: Glass 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.

Working principle of Glass electrode

Cell construction

• The glass electrode consists of a glass tube made up of a special type of glass with
high electrical conductivity.
• The glass tube contain a solution of concentration C1 (0.1M HCl)
• An Ag-AgCl electrode is placed inside the solution which acts as 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

Diagram

Working

• The potential developed across the membrane by the exchange of ions is known
as boundary potential Eb = E2– E1. Where E1 and E2 are the potential developed
at outer and inner membrane respectively.

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• 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 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 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

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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.

Three are two types of reference electrodes

1. Primary reference electrode

Example: Standard hydrogen electrode

2. Secondary reference electrode

Example: Calomel electrode

Calomel electrode
Construction

• 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

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Diagram

Working

Calomel electrode behaves as anode or cathode depending upon the nature of another
electrode.
When it acts as anode, oxidation takes place. Thus, the half-cell reaction is
2𝐻𝑔 + 2𝐶𝑙− → 𝐻𝑔2𝐶𝑙2 + 2𝑒−
When it acts as 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 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 of calomel electrode

1. It is used as a secondary reference electrode to measure single electrode potentials.

2. It is used in potentiometric analysis.

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Concentration cell
Definition

The concentration cells consist of identical electrodes immersed in the solutions

of the same electrolytes but with varying concentrations. Potential difference arises due
to difference in electrolyte concentration.

Diagram

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 oxidation reaction. The cathode
gains electrons through 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 the 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)

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The electrode potential for concentration cell is represented by

Ecell = ECathode - EAnode

0.0591 0.0591
=(E⁰Cathode - log C2) - (E⁰Anode - log C1)
𝑛 𝑛
In 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 problems

Q1. A concentration cell is constructed by dipping copper rods in 0.001M and 0.1 M
copper sulphate solutions. Calculate the EMF of 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+2 (C2 = 0.1M) Cu+2 (C1 = 0.001M)

0.0591 C2
Now, Ecell = log at 298K
𝑛 C1
0.0591 0.001
= log
2 0.1
= 0.0591 V

Q2. 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)

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0.0591 C2
Now, Ecell = log at 298K
𝑛 C1
0.0591 x
0.0595 = log
𝑛 0.001
x = 0.103 M

Q3. 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

Analytical Techniques:
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 Nernst equation,
𝟎.𝟎𝟓𝟗𝟏
Ecell = E° + log [M+n]
𝒏

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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 cm3 of FAS solution into a 50 cm3 beaker. Add one test tube
full of dil 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 increment of 0.5 cm3, stir well and measure the potential
after each addition. Continue the titration till the potential indicates a rapid jump with a
drop of titrant. Plot the graph of ΔE/ ΔV v/s vol. of K2Cr2O7.

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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.

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