Dr. Nagaraj P. M.Sc. Ph.D.

,
Associate Professor in Chemistry.
MODULE – 3

CORROSION AND ELECTRODE SYSTEM

SYLLABUS:

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.
___________________________________________________________________________
BLOW UP SYLLABUS:

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 of metals is the oxidation of metals to metal compounds by the surrounding
environment through chemical or electrochemical processes.

CLASSIFICATION:
1. Dry corrosion or chemical corrosion
2. Wet or electrochemical corrosion.

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ELECTROCHEMICAL THEORY OF CORROSION:
According to electrochemical theory of corrosion,
a) Galvanic cells are formed on the metal surface.
b) At the anodic region oxidation reaction takes place and the metal undergoes
corrosion.
c) At cathodic region, reduction reactions takes place.

Corrosion Reactions:
Anodic Reaction: The electrons liberated at the anodic region migrate to the cathodic region
constituting the corrosion current.

E.g.: Fe Fe+2 + 2e-

Cathodic Reactions:
(1) Hydrogen type reaction takes place in absence of oxygen

(a) In acidic medium and in the absence of O2 (b) In neutral medium and in the absence of
2H+ + 2e- H2 O2
2H2O + 2e- 2OH-+ H2

(2) Oxygen type reaction takes place in the presence of oxygen

(a) In acidic medium and in the presence of O2 (b) In neutral medium and in the
presence of O2
4H+ + O2 + 4e- 2H2O 2H2O + O2 + 4e- 4OH –

Corrosion of iron produces Fe+2 ions and OH- ions at anode and cathode sites respectively.

These ions diffuse towards each other and combine to give insoluble ferrous hydroxide Fe(OH)2
Fe+2 + 2OH- Fe (OH)2

In an oxidizing environment, it is oxidized to hydrated ferric oxide (yellow rust).

4Fe(OH)2 + O2 + 2H2O 2[Fe2O3 . 3H2O]

In the presence of limited oxygen, hydrated magnetic oxide (black rust) is formed.
3Fe(OH)2 + ½ O2 Fe3O4 .3H2O

TYPES OF WET CORROSION:

Differential metal corrosion (Galvanic corrosion)
Differential Aeration corrosion

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 1) DIFFERENTIAL METAL CORROSION (GALVANIC CORROSION)
i) When two dissimilar metals are in contact with each other a potential difference is set up
resulting in a galvanic current resulting galvanic corrosion.
ii) The metal with lower electrode potential acts as anode and undergoes corrosion.
iii) The metal with higher electrode potential acts as cathode and remains unattacked.
i) Larger the potential difference between the metals more intense is the corrosion.
e-
Eg.:
Steel screws on copper sheet.

Fe Cu
Fe2+ 2OH-

Anodic site
Cathodic site
Corrosion in a bimetallic couple.
2) DIFFERENTIAL AERATION CORROSION:
Corrosion of metal arising as a result of the formation of an oxygen concentration cell due
to uneven supply of air on the metal surface is known as differential aeration corrosion.
The part of the metal exposed to higher oxygen concentration acts as a cathodic region and
the part of the metal exposed to lower oxygen concentration acts as anodic region.
(a) WATER LINE CORROSION:
i) Area below the waterline is poorly aerated and acts as anode.
ii) The area above the waterline is well aerated and acts as cathode.
iii) Intense corrosion occurs at the anode and reduction of oxygen occurs near the waterline.
Examples:
Water Storage Steel Tank

Water - line Oxygen

Cathode

Corroded part (anode)

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 Ocean going ships
water line

Cathode part

Anode part

(b) PITTING CORROSION:

i) Pitting corrosion is a localized and accelerated corrosion, resulting in the formation of pits
or pin holes, around which the metal is relatively unattacked.
ii) When a small particle of dust gets deposited on a steel surface, the poorly aerated covered
portion acts as anode.
iii) The remaining well aerated exposed surface acts as cathode.
iv) Corrosion takes place at anode, resulting in the formation of pits.
v) The large cathode induces the small anodic area to corrode faster resulting in the
enlargement of the pit.
vi) The rate of corrosion increases once the pit is formed and covered with the corrosion
product, due to further decrease in the size of anode.
Fe2+ + 2 OH- Fe (OH)2 O
2 Fe2O3 . XH2O
H2O

Pitting Corrosion
Eg.:
Less aerated part of the machinery.
Cracks in metals which are not well aerated

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 CORROSION CONTROL
1. PROTECTIVE COATING:
The protective coating protects the metal from corrosion by acting as a barrier between the
metal and the corrosion environment.
a. METAL COATING b. INORGANIC COATING

(a) METAL COATING:

Metal coating is deposition of a protective metal over the surface of a base metal is called
metallic coating.
They are of 2 types: namely anodic coating & cathodic coating.
(i) Anodic Coating: Anodic coatings are produced by coating a base metal with more active metals
which are anodic to the base metal.
Eg.: Iron is coated with anodic and active metals like Zn, Mg, and Al.
One advantage of anodic coating is that, even if the coating is ruptured, the base metal does not
undergo corrosion. The exposed surface of the metal is cathodic with respect to the coating
metal. Therefore, anodic coating is also known as sacrificial coating.

GALVANIZATION is a process of coating a base metal surface with Zinc metal. Galvanization is
carried out by hot dipping method.
The galvanization process involves the following steps.
(1)The metal surface is washed with organic solvents to remove organic matter on the surface
(2) Rust and other deposits are removed by washing with dilute sulphuric acid.
(3) Finally it is washed well with water and air-dried.
(4) The article is then passed through NH4Cl flux to increase the surface activity.
(5)Then article is passed through molten zinc, maintained at 450C and then through the flux of
ammonium chloride to prevent the oxidation of molten zinc.
(6)The excess Zinc on the surface is removed by passing through a pair of hot rollers, which wipes
out excess of Zinc coating and produces a thin coating.

Galvanization

Application: Galvanization is used to protect roofing sheets, water pipes, barbed wire, buckets etc.
Galvanized articles are not used for preparing and storing foodstuffs, since Zinc
dissolves in dilute acids producing toxic Zinc compounds.

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(b) INORGANIC COATING
In this case a surface layer of the metal is converted into a compound, by chemical or
electrochemical reactions, which forms a barrier between the base metal surface and the
corrosion environment.
ANODIZATION OF METALS:
Definition: Anodization of a metal is the anodic oxidation of the metal so as to increase the
thickness of the coherent protective oxide film on its surface.
Anodized coating is generally produced on non ferrous metals like Al, Zn, Mg and their alloys.

ANODIZATION OF ALUMINIUM.
i) Aluminium article after degreasing and polishing is used as the anode and a lead plate is used as
the cathode.
ii) The electrolyte is a mixture of chromic acid and sulphuric acid.
iii)Electrolysis is carried out using d. c. at 350 C maintaining the required current density.
iv) The oxygen liberated at the anode increases the thickness of the oxide film on the surface.
and at cathode hydrogen gas is liberated.
Anode: Oxidation 2Al + 3H2O Al2O3 + 6H+ + 6e-
Cathode: Reduction 6H+ + 6e- 3H2
________________________________________
Net reaction: 2 Al + 3H2O Al2O3 + 3H2
_______________________________________

Anodization
v) The strength and corrosion resistance of the anodized film can be increased by the sealing
process.

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 The sealing process involves heating in boiling water or steam or metal salt solutions. This
changes porous aluminium at the surface of coating into its monohydrate (Al2O3 .H2O).
vi) Anodized aluminium can also be produced in a number of coloured finishes. The anodized
article is treated with Nickel or Cobalt acetate, followed by sealing process.
vii) The article can be dyed before the sealing process.
Application:
Anodization is used for aluminium pressure cookers and cooking pots.
Aluminium window frames are anodized.

2) CATHODIC PROTECTION
Cathodic protection is the technique of making the corrosion prone metal to act as a cathode
instead of as an anode by providing electrons from an external source.
a) SACRIFICIAL ANODE METHOD:
i) More reactive metals like zinc, magnesium and aluminium and their alloys when used as
anodes, provide electrons to the corrosion prone objects and convert the anodic sites on them to
cathodic sites.
ii) The sacrificial anodes get corroded and have to be replaced periodically.
iii) The object acts as cathode and does not corrode.
Application: Buried pipe lines, ship hulls, industrial water tanks, steel rods in RCC are protected
by this method.
Advantages:
(1) The method is simple (2) Low installation cost
(3) Minimum maintenance cost (4) Does not require power supply
Disadvantage: Replacement of consumed anodes.

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CORROSION PENETRATION RATE (CPR)

The Corrosion penetration rate is the speed at which any metal or alloy deteriorates
in a specific corrosive environment through chemical or electrochemical reactions.
Mathematically,
CPR= 𝐾𝑊

𝜌𝑋𝐴𝑋𝑡

The CPR is conveniently expressed in terms of either milli-inch per year (mpy) or
millimeters per year (mm/yr)
Where, 1 mili-inch =0.001 inch

CPR in mpy CPR

mm/yr
K (constant) 534 87.6
W (weight loss after exposure time) mg mg
ρ (density of metal or alloy) g/cc g/cc
A (surface area of exposed specimen) inch2 cm2
t (exposure time in corrosive medium) hrs hrs
Note : (1m= 100 cm=1000 mm = 39.37 inches)

Problems:
1. A sheet of carbon steel one meter wide by three meters long has lost 40g to corrosion over the past six
months. Calculate the penetration rate of the steel in mm/yr units and mpy units. (Carbon steel
density=7.8g/cc)
To calculate CPR in mm/yr

Given CPR mm/yr

K 87.6
W 40g 40X1000 mg
ρ 7.8g/cc 7.8 g/cc
A 1mx3m=3m2 3x100X100 cm2
t 6 months 6x30X24 hrs

CPR= KW/ ρ A t
= 87.6 x 40 x1000/ 7.8 x 3x 100 x 100 x 6 x30 x 24
= 3.466 x 10-3 mm/yr

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 To calculate CPR in mpy
Given CPR in mpy
K 534
W 40g 40 x 1000 mg
ρ 7.8g/cc 7.8 g/cc
A 1mx3m=3m2 3 x1550 inch2
t 6 months 6 x 30 x 24 hrs

CPR= KW/ ρ A t
= 534 x 40 x 1000/7.8 x 3x 1550 x 6 x 30 x 24

= 0.1363 mpy

2. A piece of corroded steel plate was found in a submerged ocean vessel, it was estimated that
the original area was 10in2 that approximately 2.6kg had corroded away during the submersion.
Assuming a corrosion penetration rate of 200mpy for this alloy in sea water, estimate the time in
years, density of steel 7.9g/cc.

Given CPR in mpy

K 534
W 2.6kg 2.6 x 1000 x1000 mg
ρ 7.9g/cc 7.9 g/cc
A 10 inch2 10 inch2
t X X hrs

CPR= 𝐾𝑊 and t= 𝐾𝑊
𝜌𝑋𝐴𝑋𝑡 𝜌𝑋𝐴𝑋𝑐𝑝𝑟

t = 534𝑋2.6𝑋106 / 7.9𝑋10𝑋 200 = 87873.42 hrs

t=87873.41 = 10.03𝑦𝑟𝑠
365𝑋24

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Yenepoya Institute of Technology, Thodar, Moodbidri-574227, Mangalore Taluk.

3. Calculate the CPR in both mpy and mm/yr for a thick steel sheet of area 100 in2 which
experiences a weight loss of 485g after one year. (density of steel=7.9g/cm3).

Given CPR in mpy

K 534
W 485g 485 x1000 mg
ρ 7.9g/cc 7.9 g/cc
A 100 in2 100 inch2
t 1 yr 365 X 24 hrs

CPR= KW/ ρ A t

= 534 x 485 x 1000/7.9 x 100x 365x 24

=37.424mpy

Given CPR in mm/yr

K 87.6
W 485g 485 x1000 mg
ρ 7.9g/cc 7.9 g/cc
A 100 in2 100 x 6.45cm2
t 1 yr 365 x 24 hrs

CPR= KW/ ρ A t

= 87.6 x 485 x 1000/7.9 x 100 x 6.45 x 365x 24

=0.9518mm/yr
ELECTRODE SYSTEM:

Electrode systems are electrochemical systems which contain two or more electrodes.

TYPES OF ELECTRODES:
1) Metal- Metal ion Electrode: It consists of metal in contact with the solution of its own
ions.
Example: Zinc electrode Zn|Zn2+

2) Amalgam Electrode: It consists of metal amalgam in contact with metal ion solution.
Example: Lead amalgam Electrode Pb-Hg|Pb+2

3) Metal- metal salt ion electrode (Metal- insoluble salt electrode): It consist of metal in
contact with a sparingly soluble salt of the same metal dipped in a solution containing anion
of the salt.
Example: Saturated calomel electrode Pt|Hg|Hg2Cl2|KCl(sat)

4) Gas Electrode: It consists of a gas bubbling about an inert metal wire or foil immersed in
a solution containing ions to which the gas is reversible.
Example: Standard hydrogen electrode Pt| H+ (1M) | H2 (1 atm)

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5) Oxidation – Reduction Electrode (Redox): It consists of an inert electrode that picks up

the potential developing due to presence of oxidized & reduced forms of the same substance
in solution.
Example: Platinum electrode Pt| Fe2+, Fe3+

6) Ion selective electrodes: Ion selective electrode is the electrode which develops potential due
to the presence of specific ion in a solution containing a mixture of ions.
Ion selective membranes are used in ion selective electrodes. Hence, ISE are also known as
membrane electrodes.

Eg: Glass electrode Ag|AgCl|HCl (0.1M)|Glass

Fluoride ion selective electrode based on LaF3 Crystal.

REFERENCE ELECTRODES:
These are the electrodes of constant potential and are used to measure the electrode potential of other
electrodes.

Secondary reference electrodes:

These are the electrodes, whose potentials are measured on H2 scale and are used to measure
the electrode potential of other metals.
Example: Calomel electrode
CALOMEL ELECTRODE OR MERCURY- MERCUROUS CHLORIDE ELECTRODE:
Construction: It consists of inner narrow glass tube and outer glass tube each having porous plug at
the bottom. Inner narrow glass tube consists of platinum wire of which one end is dipped in mercury,
placed above the paste of mercurous chloride and mercury. The narrow glass tube is placed inside an
outer glass tube. The KCl solution is filled through the side tube near the top of the outer glass tube.
The porous plug at the bottom of outer glass tube acts as salt bridge.

Representation: Pt|Hg|Hg2Cl2|KCl(sat)

Working:
Reduction
The reaction involved is, Hg2Cl2 + 2e- 2Hg + 2Cl-
Oxidation

E calomel = E0 -0.0591 log[Cl-]

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The potential of calomel electrode is measured with respect to SHE.

KCl Solution 0.1 N 1N Saturated
Electrode Potential (V) 0.334 0.280 0.2422
Potential of mercury – mercurous chloride electrode varies inversely with the concentration of
chloride ions.
Applications:
1) Used as a secondary reference electrode to measure electrode potential of the other
electrodes.
2) Used to measure pH of the given solution.

ION SELECTIVE ELECTRODES: Ion selective electrode is the electrode which develops
potential due to the presence of specific ion in a solution containing a mixture of ions.
Ion selective membranes are used in ion selective electrodes. Hence, ISE are also known as
membrane electrodes.

Eg: Glass electrode Ag|AgCl|HCl (0.1M)|Glass

GLASS ELECTRODE: Glass electrode develops potential due to the presence of H+ ion in a
solution containing a mixture of ions.

Construction:
Glass Electrode consists of a glass bulb of pH sensitive glass membrane sealed onto one end of
glass tube. It contains Ag-AgCl electrode as internal reference electrode. The glass electrode is filled
with 0.1 M HCl solution.

Glass electrode is represented as

Ag|AgCl|HCl (0.1M)|Glass

Working:
The reaction involved is, H+(Analyte) + Na+ Gl-(Glass) Na+(Analyte) + H+ Gl-(Glass)

The potential of Glass Electrode is given by

Eg= EM + Eref + E asym

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i) EM is the potential developed by the glass membrane,

EM = E1 – E2
Where E1 and E2 are the potentials appearing at the two surfaces of the glass membrane.

Where is the standard potential of the glass membrane.

C1 is the concentration of analyte solution.
C2 is the concentration of internal standard solution = 0.1 M
n=1
EM = 0.0591 log C1 -0.0591 log C2

EM = L + 0.0591 log C1, Where L is a constant = - 0.0591 log C2

ii) The Eref is the potential developed by Ag- AgCl electrode in contact with 0.1M HCl solution.
iii) E asym is the potential developed due asymmetry of outer surface of glass membrane.

Hence Eg= L + 0.0591 log C1 + Eref + E asym

Eg = E0g + 0.0591 log C1 Where E0g is a constant = L+ Eref + E asym

Eg = E0g – 0.0591 (-logC1)

Eg = E0g – 0.0591 pH Where -logC1 = - log[H+] = pH

Applications
1) Used to measure pH of the given solution.
2) Specialized glass electrode is used to measure the concentration of sodium.

MEASUREMENT OF pH OF THE GIVEN SOLUTION USING GLASS ELECTRODE:

During the measurement of the pH of the given solution, a galvanic cell is constructed comprising
the given glass electrode indicator electrode (Anode) and saturated calomel electrode as reference
electrode (Cathode). Emf of this cell is measured using a potentiometer.
Cell representation:
Ag |AgCl | HCl (0.1M) | Glass | test solution || KCl(satd.) |Hg2Cl2 | Hg|Pt

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Working:
Ecell = Ecathode – E anode
E cell= E SCE – Eg
Ecell = ESCE – [E0 g – 0.0591pH]
E cell= 0.2422- E0g + 0.0591 pH

pH = E cell - 0.2422+ E0g

0.0591

Evaluation of E0g

The above cell assembly is placed in a solution of known pH and emf of the cell is measured
using a potentiometer
E0g = 0.0591 pH + 0.2422 – E cell

Evaluation of Eog is essential since it varies with glass electrode and the reference electrode.

CONCENTRATION CELLS: Two like electrodes immersed in electrolytes containing its own
ions of varying concentrations or two like electrodes at different concentrations dipped in the same
solution of electrolyte constitutes a concentration cell.
Electrolyte concentration cells:
Two like electrodes immersed in electrolytes containing its own ions of varying concentrations
constitutes a concentration cell.
1. The driving force for the cell reaction is the tendency for the solution concentrations to
become equalized.
2. There is transfer of material from a higher concentration to a lower concentration, with
decrease in free energy and electrical energy is derived.
3. Concentration cell is represented as

M | Mn+ (C1 M) || Mn+ (C2 M) | M

Copper concentration cell: Cu | Cu2+ (C1 M) || Cu2+ (C2 M) | Cu

Eg:
Silver concentration cell: Ag | Ag+ (C1 M) || Ag+ (C2 M) | Ag
4. Emf of a concentration cell:
Consider a concentration cell,

The reactions taking place in a concentration cell is ,

At anode, M Mn+ (C1 M) + ne-
At cathode, Mn+ (C2 M) + ne- M
n+ n+
Net cell reaction is, M (C2 M) M (C1 M)

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Emf of the cell is given by ,

Ecell= log

Numerical problems:
1. A Concentration cell was constructed by immersing two silver electrodes in 0.05M
and 1M AgNO3 solution. Write the cell representation , cell reactions and calculate
the emf of the cell.

Solution: Cell representation,

Ag | AgNO3 (0.05M) || AgNO3 (1M) | Ag

At anode; Ag Ag + (0.05M) + e-
At cathode; Ag + (1M)+ e- Ag
----------------------------------------------------------------------
Net cell reaction , Ag + (1M) Ag + (0.05M)

Ecell = log , n= 1, C2 = 1.0M, C1=0.05 M

Ecell = log = 0.0768 V

2. The Spontaneous Galvanic cell Tin | Tin ion (0.024M) ‖ Tin ion (0.064M) | Tin
develops an emf of 0.0126 V at 250C, Calculate the Valency of Tin.

Solution: Ecell = log , n= log ,

Ecell = 0.0126V, C2 = 0.064 M, C1=0.024 M, n = log = 1.998

n~ 2 , Valency of Tin is 2

3. The emf of cell Cd |CdSO4(0.0093M) || CdSO4(xM)| Cd is 0.086V at 250C. Find the value of
X.
Solution: n= 2, C2 = x M, C1=0.0093 M

Ecell = 0.086 V

Ecell = log , 0.086 = log

log = 2.910, log x – log 0.0093 = 2.910

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Yenepoya Institute of Technology, Thodar, Moodbidri-574227, Mangalore Taluk.

Log x =0.878, X= antilog 0.878 = 7.55M

4. Calculate the emf of Copper concentration cell at 25 0 C, where the copper ions ratio
in the cell is 10.

Solution: n= 2, = 10

Ecell = log ,

Ecell = 0.0591 log 10 = 0.0296 V

2

ANALYTICAL TECHNIQUES:

Analytical technique is a method used to determine a chemical or physical property of a

chemical substance, chemical element, or mixture. There is a wide variety of techniques used
for analysis

Eg: Conductometry

Potentiometry

THEORY, INSTRUMENTATION AND APPLICATIONS OF POTENTIOMETRY:

Theory: Potentiometry is an instrumental method of analysis used to determine the

concentration of a substance in a solution by measuring the potential difference between
reference and indicator electrodes dipped in the solution and combined to form a galvanic
cell.

The electrode potential of the indicator electrode, for a redox reaction is given by Nernst’s
equation.

at 25 oC

Where Eo is the standard electrode potential and ‘n’ is the valency of the ions. During
titration, concentration of ions changes. Hence potential of the electrode changes. There is a
sudden change in potential at the equivalence point, when emf is plotted against volume of
the titrant.

Instrumentation: It consists of a reference electrode, an indicator electrode and a

potentiometer.

The analyte is taken in the beaker and titrant is added from micro burette. Magnetic stirrer
is used to stir the solution.

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Micro burette

beaker

Application:
Potentiometric estimation of Mohr’s salt solution using standard potassium dichromate
solution.
Indicator electrode: Platinized platinum foil
Reference electrode: Calomel electrode.
Analyte Solution: Acidified Mohr’s salt solution.
Titrant Solution: Standard potassium dichromate solution.
When a small volume of the oxidant dichromate is added to Mohr’s salt solution, a redox
electrode is set up at the indicator electrode.
Redox electrode: Pt / Fe3+, Fe2+.
Electrode reaction:
2 2 + +
C r2O7 + 14 H+ + 6Fe (aq) 2Cr 3+ + 6Fe3 + 7H2O
(aq) (aq) (aq) (aq)
(Oxidation
numbers) 2(+ 6 ) 6(+2 ) 2(+3 ) 6(+3 )

Electrode potential:

E Fe3+, Fe2+ = E0 Fe3+, Fe2+ + at 25 oC

Observations:

1. As the titration progresses, the concentration of Fe3+ ions increases , that of

Fe2+ ion decreases and emf the cell goes on increasing.
2. At the equivalence point all the Fe2+ ions are converted to Fe3+ ions and the redox
electrode Pt / Fe3+, Fe2+ ceases to exist and the e.m.f of the cell goes on increasing quite
rapidly.
3. On addition of a slight excess of dichromate, a new redox electrode comes into
existence Pt / Cr2O72-, Cr3+ . This redox electrode has a much larger potential than the
previous redox electrode Pt / Fe3+, Fe2+. Therefore, at the equivalence point of the titration,
there is a steep rise in e.m.f, which helps to locate the equivalence point in the titration.
Location of the Equivalence point:

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1. The e.m.f. is plotted against the volume of the titrant added. The central portion of the S –
shaped curve can be taken as the end point.

e.m.f.

Volume of titrant

2 Equivalence point is noted precisely by plotting ∆E / ∆V vs volume of the titrant.

(∆E / ∆V)

V eq

Volume of Titrant

The point of inflection in the curve gives a peak at the equivalence point.

THEORY, INSTRUMENTATION AND APPLICATIONS OF CONDUCTOMETRY:

Theory: The resistance (R) of a conductor is directly proportional to the length (L) of
the conductor and inversely proportional to its area of cross section (A).
R =  L Where  is the resistivity or specific resistance of the material of the
conductor.
A
 = AR
L
Reciprocal of resistivity () is called specific conductance or conductivity (K).
K = LC Where conductance, C = 1/R
A

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Yenepoya Institute of Technology, Thodar, Moodbidri-574227, Mangalore Taluk.

Conductivity (specific conductance) of an electrolyte solution (K) is the electrical conductance of the

electrolyte solution placed between two parallel platinum plates coated with platinum black of area of

cross section1cm2 and placed 1cm apart.

L/A is a constant for a given conductivity cell known as cell constant.

K = cell constant x Conductance.

Instrumentation:
It consists of a conductivity cell made up of two platinum electrodes and a
conductivity meter. The two electrodes have unit area of cross section and are placed unit
distance apart. The analyte is taken in the beaker and titrant is added from micro burette.
Magnetic stirrer is used to stir the solution.

Micro burette

beaker

Application: Estimation of a weak acid

Eg: Titration of CH3COOH vs NaOH
During titration the conductance of the solution first increases slightly till the
neutralization of weak acid (CH3COOH + NaOH CH3COONa +H2O, ionization of
sodium acetate), and hereafter increases rapidly (due to presence of highly mobile OH-
ions).

V ml is the volume of base required to neutralize weak acid.

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Yenepoya Institute of Technology, Thodar, Moodbidri-574227, Mangalore Taluk.

QUESTION BANK

BTL L 1 Questions
1. Define the term corrosion.
2. Define metallic corrosion.
3. Define differential aeration corrosion.
4. What is anodic metal coating?
5. What is anodizing?
6. What is cathodic protection?
7. What are reference electrodes?
8. What are Ion selective electrodes?
9. What are Concentration cells ?
BTL L2 Questions
10. Discuss the corrosion of iron based on electrochemical theory.
11. Explain the differential metal or galvanic corrosion with examples.
12. Explain differential aeration corrosion with suitable example.
13. Write a note on galvanization.
14. Explain anodizing of aluminium.
15. Explain sacrificial anode techniques for prevention of corrosion.
16. Discuss the construction, working and applications of calomel electrode.
17. Discuss the different types of electrodes with example.
18. Discuss the Construction and working of glass electrode.
19. Discuss the determination of pH using glass electrode.
20. Write a note on Electrolyte concentration cells.
21. Discuss the theory, instrumentation and application for the estimation of iron using
potentiometry.
22. Discuss the theory, instrumentation and application for the estimation of weak acid
using conductometry.

BTL L3 Questions
23. Explain what type of corrosion occurs when
i) Steel pipe is connected to copper plumbing or Copper nut is in contact with iron
bolt [Differential metal (Galvanic) Corrosion.]

ii) Presence of small dust particles on iron surface for a long time [Differential
aeration.]

24. Account for the following:

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Yenepoya Institute of Technology, Thodar, Moodbidri-574227, Mangalore Taluk.

i) Zn in contact with Ag undergoes corrosion faster than Zn in contact with Cu.

(Greater the difference in their positions in galvanic series, faster is the rate of
corrosion at anode. There greater difference in position between Zn and Ag
compared to Zn and Cu in galvanic series.)

ii) The hull of a ship suffers from severe corrosion, when partially dipped in sea
water.( differential aeration corrosion - water line corrosion).

25. Explain why pinholes on tin coated iron are more prone to corrosion than pinholes
on zinc coated iron.
(Galvanization is a anodic (sacrificial) coating where as tinning is a cathodic
coating.)
26. Explain why Galvanized iron sheets are more preferable than tin coated iron sheets.
(Galvanization is an anodic (sacrificial) coating where as tinning is a cathodic
coating.)

27. A sheet of carbon steel one meter wide by three meters long has lost 40g to corrosion
over the past six months. Calculate the penetration rate of the steel in mm/yr units
and mpy units. (Carbon steel density=7.8g/cc)
28. A piece of corroded steel plate was found in a submerged ocean vessel, it was
estimated that the original area was 10in2 that approximately 2.6kg had corroded away
during the submersion. Assuming a corrosion penetration rate of 200mpy for this
alloy in sea water, estimate the time in years, density of steel 7.9g/cc.
29. Calculate the CPR in both mpy and mm/yr for a thick steel sheet of area 100 in2
which experiences a weight loss of 485g after one year. (density of
steel=7.9g/cm3).
30. A Concentration cell was constructed by immersing two silver electrodes in 0.05M
and 1M AgNO3 solution. Write the cell representation , cell reactions and calculate
the emf of the cell.

31. The Spontaneous Galvanic cell Tin | Tin ion (0.024M) ‖ Tin ion (0.064M) | Tin
develops an emf of 0.0126 V at 250C, Calculate the Valency of Tin.

32. The emf of cell Cd |CdSO4(0.0093M) || CdSO4(xM)| Cd is 0.086V at 250C. Find the
value of X.

33. Calculate the emf of copper concentration cell at 250 C, where the copper ions ratio in
the cell is 10.

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