Applied Chemistry for CSE stream BCHES202

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 Chemistry

The term corrosion is used to denote a change. A metal changes from its elementary state to the
combined state when it comes in contact with liquid medium. This is actually due to the chemical
interaction between the metal and the environment.

Definition: “The spontaneous deterioration and consequent loss of a metal/alloy due to

chemical/electrochemical attack by the environment”.

Example: When iron metal is exposed to the moist environment, the metal forms a hydrated ferric
oxide called rust which is relatively non-protective.

Most of the corrosion cases are electrochemical in nature taking place by an electrochemical attack
on the metal in the presence of air and moisture (H2O) called wet corrosion. The mechanism of
the wet corrosion is explained on the basis of electrochemical theory of corrosion.

Electrochemical theory of corrosion:

According to this theory,

1. When a metal is in contact with moist air or when dissimilar metals are contact with each
other in a solution, large numbers of galvanic cells are formed with the existence of anodic and
cathodic area on the metal.
2. In this corrosion, oxidation of the metal and reduction of species present in solution takes
place.

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3. The anodic part of the metal undergo oxidation and suffers from corrosion, cathodic part
undergo reduction and protected from corrosion.
4. The electrons are transferred through the metal from anode to cathode.
5. During corrosion the following reactions takes place.

At anode (oxidation reaction) : 𝑀 → 𝑀n+ + 𝑛𝑒–

The reaction at cathode (reduction reaction) depends on the nature of the environment: If the
medium is acidic,
1
In the presence of dissolved oxygen: 2𝐻+ + 𝑂2 + 2𝑒– → 𝐻2𝑂
2

In the absence of dissolved oxygen: 2𝐻+ + 2𝑒– → 𝐻2

If the medium is alkaline/neutral,

1
In the presence of dissolved oxygen: 𝐻2𝑂 + 𝑂2 + 2𝑒– → 2𝑂𝐻–
2

In the absence of dissolved oxygen: 2𝐻2𝑂 + 2𝑒– → 2𝑂𝐻– + 𝐻2 ↑

Example: Rusting of an Iron in the presence of moist air Anodic

Reaction: 𝐹𝑒 → 𝐹𝑒2+ + 2𝑒–

Cathodic reaction 1 – –
∶ 𝐻2𝑂 + 2 𝑂2 + 2𝑒 → 2𝑂𝐻

Products of anode & cathode: 𝐹𝑒2+ + 2𝑂𝐻– → 𝐹𝑒(𝑂𝐻)2

1
In the presence of oxygen: 2𝐹𝑒(𝑂𝐻) 2 + 𝑂2 → 𝐹𝑒2𝑂3. 2𝐻2𝑂
2
(Rust)
Types of corrosion:

Corrosion can be classified into 2 types as follows

1) Differential metal corrosion (Galvanic corrosion)
2) Differential aeration corrosion

Differential metal corrosion (Galvanic corrosion)

1) When two dissimilar metals are in direct contact with one another and exposed to a corrosive
medium, the metal with lower electrode potential becomes anode and suffers from corrosion,
whereas the metal with higher electrode potential becomes cathode and protected from corrosion.
This type of corrosion is known as differential metal corrosion or galvanic corrosion.

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2) The rate of corrosion depends mainly on the difference in the position of the two metals in
galvanic series.
3) Higher the difference, faster is the rate of corrosion.

Example: Electrode potential of iron (-0.44 V) is less than that of copper (0.34 V). Therefore when
iron is in contact with copper, iron becomes anodic and undergoes corrosion, whereas copper
becomes cathodic and protected from the corrosion.

𝐴𝑡 𝐴𝑛𝑜𝑑𝑒: 𝐹𝑒 → 𝐹𝑒2+ + 2𝑒–

1
𝐴𝑡 𝐶𝑎𝑡ℎ𝑜𝑑𝑒 ∶ 𝐻2𝑂 + 2 𝑂2 + 2𝑒 – → 2𝑂𝐻–

𝐹𝑒2+ + 2𝑂𝐻– → 𝐹𝑒(𝑂𝐻)2

1

2𝐹𝑒(𝑂𝐻)2 + 2 𝑂2 → 𝐹𝑒2𝑂3. 2𝐻2𝑂

Differential aeration corrosion

1) When a metal is exposed to different concentration of air (O2), part of the metal exposed to
lower concentration of O2 becomes anodic and undergoes corrosion.
2) Other part of the metal exposed to higher concentration of O2 becomes cathodic and
protected from the corrosion.
3) The difference in O2 concentration produces a potential difference and causes corrosion.
This type of corrosion is called differential aeration corrosion.

Example: 1 Water line corrosion

1) It is observed in steel or iron water tank partially filled with water. Part of the tank just
below water level is exposed to lower concentration of O2 becomes anodic and undergoes
corrosion.
2) Part of the tank above the water line which is exposed to higher concentration of O2
becomes cathodic and protected from the corrosion.

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3) More corrosion is observed just below the water line; hence this type is called water line

corrosion.

Reactions:
𝐴𝑡 𝐴𝑛𝑜𝑑𝑒: 𝐹𝑒 → 𝐹𝑒2+ + 2𝑒–
1
𝐴𝑡 𝐶𝑎𝑡ℎ𝑜𝑑𝑒 ∶ 𝐻2𝑂 + 2 𝑂2 + 2𝑒 – → 2𝑂𝐻–

1
𝐹𝑒2+ + 2𝑂𝐻– → 𝐹𝑒(𝑂𝐻)2 , 2𝐹𝑒(𝑂𝐻)2 + 2 𝑂2 → 𝐹𝑒2𝑂3. 2𝐻2𝑂

Example: 2 pitting corrosion

1. Pitting corrosion is observed when dust particles get deposited over the metal surface.
2. The portion of the metal covered by dust which is less aerated becomes anodic and suffers
from corrosion.
3. Thus, metal is lost below the surface of dust particle forming a deep and narrow pit.
4. The adjacent area of the metal which is exposed to higher concentration of O2
becomes cathodic and protected from corrosion.

Reactions:
𝐴𝑡 𝐴𝑛𝑜𝑑𝑒: 𝐹𝑒 → 𝐹𝑒2+ + 2𝑒–
1
𝐴𝑡 𝐶𝑎𝑡ℎ𝑜𝑑𝑒 ∶ 𝐻2𝑂 + 2 𝑂2 + 2𝑒 – → 2𝑂𝐻–

𝐹𝑒2+ + 2𝑂𝐻– → 𝐹𝑒(𝑂𝐻)2

1

2𝐹𝑒(𝑂𝐻)2 + 2 𝑂2 → 𝐹𝑒2𝑂3. 2𝐻2𝑂

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Corrosion Control:
Galvanization

Coating of zinc on iron or steel by hot dipping process is called galvanizing. (M.P of Zn=419 °C)
It is carried out as follows,

The iron sheet is subjected to pretreatment by degreasing with organic solvent.

1) The sheet is passed through dilute H2SO4 to remove any rust.
2) Washed with distilled water and dried by supplying hot air.
3) Then iron sheet is dipped in molten bath of Zn at 419°C and surface is covered with NH4Cl
flux which prevents the oxidation of Zn metal.
4) The excess of coated metal is removed by passing through a pair of hot rollers and cooled
gradually.

Anodizing
Anodizing is the process of oxidation of outer layer of metal to its metal oxide by electrolysis.
Oxide layer formed over the metal itself acts as protective layer.

Anode : Aluminium

Cathode : Steel or Copper

Electrolyte : 5-10% chromic acid

Temperature : 30-40 °C

Applied potential : 0-40 V

Aluminum is made as anode and copper or steel is used as cathode. The electrodes are immersed
in an electrolyte consisting of 5-10% chromic acid. The temperature is maintained at 30-40 °C.
Potential of 0-40 V is applied which oxidizes outer layer of Al to Al2O3 and that get deposited over
the metal. The reactions involved are as follows

𝐴𝑡 𝐴𝑛𝑜𝑑𝑒: 2𝐴𝑙(𝑠) + 3𝐻2𝑂(𝑙) → 𝐴𝑙2𝑂3(𝑠) + 6𝐻+ + 6𝑒–

𝐴𝑡 𝐶𝑎𝑡ℎ𝑜𝑑𝑒: 6𝐻+ + 6𝑒– → 3𝐻2(𝑔)
𝑂𝑣𝑒𝑟 𝑎𝑙𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛: 2𝐴𝑙(𝑠) + 3𝐻2𝑂(𝑙) → 𝐴𝑙2𝑂3(𝑠) + 3𝐻2(𝑔)

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The anodized coatings are thicker than the natural oxide film and possess improved corrosion
resistance as well as resistance to mechanical injury.

Sacrificial anodic protection:

1) The metal to be protected is connected to a more anodic metal using a metallic wire.
2) The more active metal gets corroded while the parent structure is protected from corrosion.
3) The more active metal so employed is called sacrificial anode.
4) The sacrificial anodes to be replaced by fresh ones as and when it is required.
5) Commonly used sacrificial anodes are: Mg, Zn, Al etc.

Example: steel pipe is protected by connecting it to a block

of Zn. In such cases steel acts as a cathode and is unaffected
or protected from corrosion and Zn act as anode and
undergoes sacrificial corrosion.

Corrosion Penetration Rate (CPR)

The corrosion penetration rate (CPR) is defined as “the speed at which any metal in a specific
environment deteriorates due to chemical reactions when it is exposed to a corrosive environment”
or the amount of corrosion loss per unit time in thickness or the speed at which corrosion spreads
to the inner portions of a material. Corrosion rate depends on the metal and the environmental
condition.
The CPR is given by
k×W
CPR =
D×A×T
Where k = a constant
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

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The corrosion penetration rate is expressed in terms of thickness or weight loss when the surface of
the metal corrodes uniformly across an area.
This method involves the exposure of a weighed piece of test metal or alloy to a specific
environment for a specific time. This is followed by a thorough cleaning to remove the corrosion
products and then determining the weight of the metal after corrosion.
The rate may vary if the rate expressed by the formula above is used to compare corrosion rates for
a period longer than one year with rates calculated over short periods. This is because the short time
periods are prone to fluctuating environmental changes from season to season and from day to day.
Note:-
Unit of CPR is mils per year if W is in mg, A in Inch2, D in g/cm3, t in hrs and k value will be 534.
(1mil = 0.001 inch)
Unit of CPR is mm per year if W is in mg, A in cm2, D in g/cm3, t in hrs and k value will be 87.6.
(1inch = 2.54 cm)
If CRP is less than 20m/year or 0.5 mm/year, it is acceptable for most of the application.

Electrode System
Types of electrodes:
1. Metal-metal ion exchange: In this electrode, a metal is immersed in the ionic solution of its
own salts
Example: Cu/Cu2+
2. Redox electrode: In this electrode, ions of a chemical species in two different oxidation states
are in contact with each other
Example: Pt
3. Gas Electrode: In this electrode, an inert metal like platinum is in contact with gas molecules
Examples: Standard Hydrogen electrode
4. Metal-Insoluble salt electrode: In this electrode, metal is in contact with its insoluble salt
Example: Calomel Electrode
5. Amalgum electrode: In this electrode, a known concentration of metal dissolved in liquid
mercury is in contact with ionic solution of the metal
Example: Pb(Hg)
6. Ion selective electrode: This electrode is more selective towards a particular type of ion in
the mixture.
Example: Glass electrode

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Ion-selective electrode
The electrode, which are responds to a specific ion in a mixture by ignoring other ions are called
as ion selective electrodes. They consist of a thin membrane in contact with ion solution. Example,
glass electrode
Glass Electrode:
This electrode works on the principle that when a thin, low resistivity glass membrane is in contact
with a solution containing H+ ions, a potential develops across the membrane and the solution.
Potential developed depends on the concentration of hydrogen ions in the solution.

Construction:

➢ It consists of a long glass tube with a thin-walled glass bulb containing 0.1 M HCl [C1].

➢ Ag/AgCl electrode placed inside the solution to provide electrical contact.

➢ The glass electrode is dipped in unknown solution of concentration C2.

➢ The potential developed across the membrane by the exchange of ions with the composition of
glass is known as the boundary potential Eb (E2 – E1).

➢ Even when C1=C2 , E≠ 0 a small potential is developed across the membrane, it is called as

asymmetric potential (Easy).

Cell representation: Ag / AgCl / HCl (0.1M) / unknown solution/ Glass

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Working:
E1 & E2 is the potential developed at outer and inner membrane respectively the boundary
potential is, 𝐸b = 𝐸2 − 𝐸1
0.0591 0.0591
𝐸 = 𝐸0 + log[𝐶2] − {𝐸0 + log[𝐶1] }
b 𝑛 𝑛

𝐸 = 0.0591 log[𝐶2] – 0.0591 log[𝐶1]

b n n

0.0591 0.0591 1
𝐸b = log[𝐶2] + 𝑙𝑜𝑔
𝑛 𝑛 [𝐶1]

Where 𝐿 = 0.0591 𝑙𝑜𝑔__1__

n [C1]

Therefore
0.0591
𝐸b = 𝐿 + log[𝐶2]
𝑛
Here n=1, [C2] = [H+] ions in outer membrane, Then
𝐸b = 𝐿 + 0.0591log [𝐻+]
𝐸b = 𝐿 − 0.0591𝑝H (pH= -log[H+] )
The Glass electrode potential is given by
𝐸G = 𝐸b + 𝐸Ag/AgCl + 𝐸Asy

Substitute the value of Eb

𝐸G = 𝐿 − 0.0591𝑝H + 𝐸Ag/AgCl + 𝐸Asy

Consider𝐿1 = 𝐿 + 𝐸Ag/AgCl + 𝐸Asy, Therefore

𝐸G = 𝐿1 − 0.0591𝑝H

Determination of pH of a solution 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

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

The emf of a cell is determined by using voltmeter.

Ecell is the difference b/w glass electrode potential EG and the calomel electrode potential ESCE.

𝐸Cell = 𝐸Cathode − 𝐸Anode

𝐸Cell = 𝐸G − 𝐸SCE
𝐸Cell = 𝐿1 − 0.0591𝑝H − 𝐸SCE
𝐾 − 𝐸Cell
PH = [𝐾 = 𝐿1 − 𝐸SCE]
0.0591

Where K= Electrode assembly constant.

Reference electrodes
Reference electrodes are the electrodes whose potential is known and used for determination of
potential of unknown electrodes
Calomel Electrode:
Construction:
➢ Calomel electrode consists of long glass tube with two side tubes.

➢ One at the top to fill saturated KCl solution and the other side tube is connected to the salt
bridge. Mercury is placed at the bottom which is covered with a layer of Hg and Hg2Cl2
(calomel) paste.

➢ The remaining portion is filled with saturated KCl solution.

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➢ A platinum wire is dipped into the mercury and is used to provide external electrical
contact.

➢ The calomel electrode is represented as, Cl-/Hg2Cl2/Hg

Working:

Calomel electrode behaves as anode or cathode depending upon the nature of another electrode.
The half-cell reaction when it acts as an anode is

2𝐻𝑔 + 2𝐶𝑙– → 𝐻𝑔2𝐶𝑙2 + 2𝑒–

The half-cell reaction when it acts as a cathode is
𝐻𝑔2𝐶𝑙2 + 2𝑒– → 2𝐻𝑔 + 2𝐶𝑙–
The electrode reaction is,
𝐻𝑔2𝐶𝑙2 + 2𝑒– ↔ 2𝐻𝑔 + 2𝐶𝑙–
Applying Nernst equation,
0.0591 [𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠]
E = 𝐸0 + 𝑙og
𝑛 [𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠]

0.0591 [𝐻𝑔2𝐶𝑙2]
E = 𝐸0 + 𝑙𝑜𝑔
𝑛 [𝐻𝑔]2[𝐶𝑙]2–
Since [Hg2Cl2] = [Hg] 2 = 1, the above equation becomes
0.0591 1
𝐸 = 𝐸0 + log –
2 [𝐶𝑙 ]

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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)

The potential of calomel electrode is measured with respect to SHE and it depends on
concentration of KCl solution used.

Conc. KCl 0.1N 1N Saturated KCl

Potential (V) 0.334V 0.281V 0.242V

Applications:
✓ Used to determine the potential of the other electrodes.
✓ It is commonly used as reference electrode in all potentiometric determinations.

Electrolytic Concentration Cell:

It is galvanic cell, which consists of two identical electrodes, which are in contact with the same
solution of electrolyte in different concentrations.

Example:

Consider two silver electrodes that in contact with the AgNO3 solution of different concentrations
(M1 and M2) connected through voltmeter. The electrolytes are connected through salt bridge.

The cell representation Ag/ AgNO3 (M1)// AgNO3 (M2)/Ag

Where M1 and M2 are the molar concentration of the Ag+ ions in the two half-cells.

𝐴𝑡 𝐴𝑛𝑜𝑑𝑒: 𝐴𝑔 → 𝐴𝑔+(𝑀1) + 𝑒–

𝐴𝑡 𝐶𝑎𝑡ℎ𝑜𝑑𝑒: 𝐴𝑔+(𝑀2) + 𝑒– → 𝐴𝑔

𝑁𝑒𝑡 𝐶𝑒𝑙𝑙 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛: 𝐴𝑔+(𝑀2) ↔ 𝐴𝑔+(𝑀1)

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Apply Nernst equation for the cell reaction,

0.0591 [𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠]
𝐸 = 𝐸0 + 𝑙𝑜𝑔
𝑛 [𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠]

𝐸0 = 𝐸0Cathode − 𝐸0Anode

Since both anode & cathode is made up of same metal, 𝐸0 = 0

0.0591 [𝑀2] 0.0591 [𝑀2]

𝐸=0+ 𝑙𝑜𝑔 𝑜𝑟 𝐸 = 𝑙𝑜𝑔

𝑛 [𝑀1] 𝑛 [𝑀1]

Analytical Techniques:
Potentiometric Titration
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
𝐸 = 𝐸0 + 𝑙𝑜𝑔[𝑀n+]
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 a indicator electrode (e.g.: Platinum) and an saturated reference
electrode (E.g.: Calomel electrode), stirrer & potentiometer to measure the potential values.

Emf of the solution can be measured by combining reference electrode with 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
0.5ml 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.

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Applications
1. Estimation of 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 25cm3 of FAS solution into

a 50cm3 beaker. Add one test tube full of dil H2SO4.

Immerse Pt.& calomel electrodes into the solution, &
connect the electrodes to a Potentiometer.
Fill the burette with K2Cr2O7solution.

Add K2Cr2O7 solution from the burette with increment of 0.5cm3,

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 ∆E/ ∆V v/s vol. of K2Cr2O7.
Conductometric Titration
Conductance is ease with which current flows through the solution. It is reciprocal of resistance.
C=1/R = Ω-1 or mho or siemen
Theory:
The Conductance of the solution is explained by considering ohm’s law.
According to ohm’s law the current flowing through the conductor is directly proportional to
voltage and inversely proportional to the resistance.
I= or E=IR

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The resistance of the any conductor is directly proportional to the length, inversely proportional
to the area of cross section of the conductor Therefore R = S (l/a) where S is specific resistance
Therefore C = 1/R = 1/S (a/l), K (a/l), K = specific conductance
It is defined as the conductance of the solution present between two parallel electrodes of 1cm2
area of cross section and 1cm apart.
The conductance of the solution is depending on mobility of the ion and number of the ion.
Instrumentation: It consists of two platinum electrodes each of unit area of cross section placed
at unit distance apart. The electrodes are dipped in the electrolytic solution taken in a beaker. It is
connected to a conductometer to measure the conductance. The conductance is measured after the
addition of the titrant a t interval of 0.5ml.

Types of conductance: There are three type’s namely specific conductance, equivalence
conductance, and molar conductance.

Specific conductance (K) is the conductance of the solution present between two parallel
electrodes of 1cm2 area of cross section and 1cm apart.

K = 1/R (l/a) K = Siemen m-1

Equivalence conductance (λ) is the conductance of the solution when 1g equivalent weight of
solution is placed between two electrodes of area 1cm2 at 1cm apart.

Molar conductance (µ) is the conductance of the solution when 1g molecular weight of solute is
placed between two electrodes of area 1cm2 at 1cm apart

Application of Conductometric titration

Weak acid v/s Strong base

Consider the titration of acetic acid against NaOH.

The conductance of the acid will be initially
low since acetic acid is a weak electrolyte.

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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.

𝐶𝐻3 𝐶𝑂𝑂𝐻 + 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.

Most probable questions

1. Define corrosion. Explain electrochemical theory of corrosion taking iron as example.
2. Explain the following
a. Differential metal corrosion
b. Differential aeration corrosion
c. Waterline corrosion
d. Pitting corrosion
3. Explain the process of Galvanization, Anodizing and Sacrificial anodic method.
4. What are reference electrode. Explain the construction, working and application of Calomel
electrode.
5. What is ion selective electrode. Explain the construction and working of glass electrode.
6. Explain the determination of pH using glass electrode.
7. What are concentration cell. Explain with an example
8. Numerical based on CPR and concentration cell.

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