Chemistry For CSE Stream 1

Module-3
CORROSION AND ELECTRODE SYSTEM
CORROSION
Corrosion is defined as “the destruction of metals or alloys by the surrounding
environment through chemical or electrochemical changes.”
The process of corrosion is the transformation of pure metal into its undesired metallic
compounds. The life of a metal object gets shortened by the corrosion process.
The familiar examples of corrosion are
i. Rusting of iron – a reddish brown scale formation on iron and steel objects. It
is due to the formation of hydrated ferric oxide.
ii. Green scales formed on copper vessels. It is due to the formation of basic
cupric carbonate [CuCO3 + Cu(OH)2]
Illefects of Corrosion
 Loss of efficiency.
 Contamination of product.
 Damage of metallic equipment’s.
 Inability to use metallic materials.
 Appearance as when corroded material is unpleasing to the eye.
 Loss of valuable materials such as blockage of pipes, mechanical damage of
underground water pipes.
 Accidents due to mechanical loss of metallic bridges, cars, aircrafts etc.
 Safety, for example, sudden failure can cause fire, explosion, release of toxic product,
and construction collapse.
 Depletion of Natural Resources.
 India Losses 5.7 % GDP due to corrosion.

Chemical corrosion (Dry corrosion)

Chemical corrosion occurs due to the direct chemical reaction between the metal and the
gases present in the corrosive environment. This type of corrosion is generally observed in
the absence of moisture or conducting electrolyte medium. Therefore, it is also known as
dry corrosion.
Eg: Oxidation of metals or alloys on exposure to oxygen in air. Reaction of corrosive
gases such as HCl, H2S, SO2, Cl2, F2, NH3 etc. with metal and alloy surfaces.
Electrochemical corrosion (Wet corrosion)

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Electrochemical corrosion involves reactions in aqueous medium. The conducting surface

of the metal undergoes an electrochemical reaction with the moisture and oxygen present
in the atmosphere. This process can be explained on the basis of electrochemical theory of
corrosion.
Electrochemical theory of corrosion
Electrochemical theory of corrosion can be explained taking iron as an example.

When a metal like iron is exposed to the corrosive environment according to electrochemical
theory, corrosion of metal takes place due to the formation of anodic and cathodic regions on
the same metal surface or when the two metals are in contact with each other. The electrons
released at the anodic area are taken up by the cathodic area.

Following are the changes occurring.

i) Formation of galvanic cells. Anodic and cathodic areas are formed resulting in minute
galvanic cells.
ii) At anode oxidation takes place so that metal is converted into metal ions with the
liberation of electrons and move towards cathode.
iii) Oxygen of the atmosphere is reduced to OH ¯ ions in the presence of water (moisture) at
the cathodic area.
Anodic reaction:
At the anodic area, oxidation takes place resulting in the corrosion of iron.
Fe Fe+2 + 2e-
Cathodic reactions:
Electrons flow from the anodic to cathodic area and cause reduction depending on the
nature of the corrosive environment. Since the metal cannot be reduced further, metal
atoms at cathodic region are unaffected by the cathodic reaction. Some constituents of the
corrosion medium take part in the cathodic reaction.
Most common types of cathodic reactions are either liberation of hydrogen or absorption
of oxygen.
(a) Liberation of hydrogen takes place in the absence of oxygen
(i) In acidic medium and in the absence of oxygen, hydrogen liberation takes place.
2H+ + 2e- H2↑

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(ii) In neutral or alkaline medium and in the absence of oxygen, hydroxide ions are
formed with liberation of hydrogen.
2H2O + 2e- 2OH¯ + H2↑
(b) Absorption of oxygen takes place in the presence of oxygen.
(i) In acidic medium and in the presence of oxygen.
4H+ + O2 + 4e- 2H2O
(ii) In neutral or alkaline medium & in the presence of oxygen, hydroxide ions are formed
2H2O + O2 + 4e- 4OH¯
The metal ions formed at the anode combine with the OH ¯ ions and form the insoluble
Fe(OH)2. In an oxidizing environment, it is oxidized to ferric oxide and the yellow rust is
hydrated ferric oxide.
2Fe+2 + 4OH¯ 2Fe(OH)2
4Fe(OH)2 + O2 + 2H2O 2[Fe2O3·3H2O] + H2
Yellow Rust
Types of Corrosion
Differential Metal Corrosion (Galvanic Corrosion)
Differential metal corrosion occurs when two dissimilar metals are in contact with each
other in a corrosive conducting medium. The two metals differ in their tendencies to
undergo oxidation, the one with lower electrode potential or the more active metal acts as
anode and the one with higher electrode potential acts as cathode. The potential difference
between the two metals is the driving force for corrosion. The anodic metal undergoes
corrosion and the cathodic metal is generally unattacked.
The following reactions occur during differential metal corrosion.
At the anode : M M+n + ne-
At the cathode : Depending on the nature of the corrosion environment the cathode
reaction is either hydrogen evolution or oxygen absorption.
(i) 2H+ + 2e- H2 (g)
(ii) O2 + 2H2O + 4e- 4OH¯
For example, if a piece of iron combined with copper is exposed to corrosive atmosphere.
Iron acts as anode in the presence of copper (iron is placed above copper in the
electrochemical series). In such case, iron undergoes corrosion and copper is unaffected.

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Differential Aeration Corrosion

Differential aeration corrosion occurs when a metal surface is exposed to differential air
concentrations or oxygen concentrations, the part of the metal exposed to higher oxygen
concentration acts as cathodic region and the part of the metal exposed to lower oxygen
concentration acts as anodic region. As a result the part of the metal exposed to lower
oxygen concentration undergoes corrosion.
At the anode (less O2 concentration)
M M+n + ne- (oxidation)
At the cathode (more O2 concentration)
O2 + 2H2O + 4e- 4OH¯ (reduction)
“Corrosion of metals is due to the formation of an oxygen concentration cell because of
the uneven supply of air on the metal surface is known as differential aeration corrosion.”
Examples
i. Part of the nail inside the wall which is exposed to lower oxygen concentration than the
exposed part, undergoes corrosion.
ii. Window rods inside the frame suffer corrosion but not the exposed parts.
iii. Metal under dirt, dust, scale or water undergoes corrosion.
iv. Paper pins inside the paper gets corroded, and the exposed part is free from corrosion.
Water line corrosion and pitting corrosion are the two cases of differential aeration
corrosion.
Water Line Corrosion
Water line corrosion is observed in steel water tanks, ocean going ships etc.
The water line corrosion takes place due to the formation of differential oxygen
concentration cells. The part of the metal below the water line is exposed only to dissolved
oxygen while the part of the metal above the water is exposed to higher oxygen
concentration of the atmosphere. Thus, part of the metal below water acts as anode and
undergoes corrosion and the part above the water line is free from corrosion.

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Corrosion control
Corrosion control refers to measures that are implemented in various fields to control
corrosion in soil, metal, concrete, water and sand. This consists of different corrosion
monitoring and control techniques that can be used by industries to solve corrosion
problems according to their requirements. With such measures in place, the harmful
effects and negative consequences of corrosion can be avoided.
The methods commonly used to control corrosion of metals are
1. Protective coatings i. Inorganic coating ii. Metal coating iii. Organic coating
2. Cathodic protection
3. Anodic protection 4. Corrosion inhibitors

1. Protective coatings
The protective coating protects the metal from corrosion by acting as a barrier between the
metal and the corrosion environment.
Inorganic coating
Inorganic coatings are generally obtained by converting a surface layer of the metal into a
compound or metal oxide by chemical or electrochemical reactions, which forms a barrier
between the metal surface and the corrosion environment.
ANODIZING
Anodizing is the process of oxidising the outer layer of the metal into its metal oxide.
These are generally produced on non-ferrous metals like Al, Zn, Mg by anodic oxidation
process, in which the base metal is made as anode in an electrolytic bath of suitable
composition, and by-passing direct electric current. The most commonly used baths are
chromic acid and sulphuric acid or their mixtures. After anodizing, the oxide coating is
sealed by immersing in boiling water.
Anodizing of Aluminium involves the following steps.
The article to be anodized is degreased, thoroughly polished, connected to the anode and
steel or copper is made as the cathode. The electrolyte is 5-10% chromic acid. The

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temperature of the bath is maintained at 35ºC. The voltage is programmed to increase from
0 to 50V to maintain an anode current density of 10-20mA/cm 2. During the first 10
minutes, the potential is increased from 0 to 40V. When the potential reaches 40V,
anodizing is continued for 20 minutes. After 20 minutes the voltage is increased from 40 -
50V and held at 50V for five minutes. An opaque oxide layer of 2-8µm thickness is
obtained.

Fig 1: Anodization
The article can be coloured by immersing for about 20 minutes in an aqueous solution of
the dye stuff at 50-60ºC. Finally, the object is treated with boiling water to form
Al2O3.H2O where the pores is sealed.
Anodized articles are used as soap boxes, tiffin carriers, window frames etc.
CATHODIC PROTECTION
Corrosion of metals occurs because of the flow of electrons from the anodic to cathodic
regions. The anodic regions undergo corrosion whereas the cathodic regions are
unaffected. The principle of cathodic protection is to reverse this flow of electron. This
can be achieved by providing electrons from an external source so that the metal always
remains cathodic.
The technique by which metals are protected from corrosion by providing electrons from
an external source is called cathodic protection.
Cathodic protection can be achieved by the following method.
(i) Sacrificial anode method
Sacrificial Anode Method
In this method, the metal to be protected is converted into a cathode by connecting it to a
more active metal. This active metal acts as anode. Zinc or magnesium are the commonly
used anodes. These metals, being more active, act as anode and undergo preferential

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corrosion, protecting the metal structure. Since the anodic metals are sacrificed to protect
the metal structure, therefore the method is known as sacrificial anode method. The
sacrificial anodes which get corroded in course of time have to be replaced.
Examples
1) A magnesium block connected to a buried oil storage tank. Fig(a)
2) Mg bars are fixed to the sides of ocean-going ships to act as sacrificial anodes.
Fig(b)
3) Zn wire buried along the oil pipeline. Fig (c)

Advantages
 The cost of investment is low
 It can be easily installed and maintained.
 Provides protection without power consumptions.
Disadvantages
 Periodic replacement of anode
 Limited driving potential, hence not applicable for large objects.
Metal Coating
Corrosion of metals can be controlled by depositing a protective metal over the surface of
a base metal. This process is called metal coating. Metal coating can be anodic metal
coating or cathodic metal coating.
Anodic Metal Coating
Anodic coatings are produced by coating a base metal with more active metals which are
anodic to the base metal.
For example, iron is coated with more active metals such as zinc or magnesium. The
characteristic feature of anodic coating is that, the base metal on which coating is done
will not get corroded even if the coating is ruptured. The exposed surface of the metal is
cathodic with respect to the coating metal and the coating metal undergoes corrosion.

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Therefore, anodic coating is also known as sacrificial coating. Galvanization is an

example of anodic metal coating.

Galvanization
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 sulfuric acid.
3) Finally, the article is washed with water and dried.
4) The article is then dipped in a bath of molten zinc, maintained at 425- 430ºC and
covered with a flux of ammonium chloride to prevent the oxidation of molten zinc.
5) 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.

Galvanized articles are used in the form of roofing sheets, fencing wire, buckets, bolts,
nuts, nails, screws, pipes tubes etc.
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 a chemical
reaction in the metal when it is exposed to a corrosive environment.
The speed or rate of deterioration depends on the environmental conditions and the type and
condition of the metal under study. Corrosion penetration rate may also be known as
corrosion rate. Several pieces of data must be collected to calculate the corrosion penetration
rate for any given metal:

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 The weight lost (the decrease in weight of the metal during the period of reference).
 The density of the metal.
 The total surface area initially present.
 The time taken for the metal to corrode.

The CPR is calculated as follows:

CPR = (k x W) / (D x A x 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

The corrosion penetration rate (CPR) is best expressed in terms of thickness loss of material
per unit time. It is expressed in mpy (mils per year) or mm/year (milimeter per year).

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 lost metal due to corrosion.

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ELECTRODE SYSTEM
Electrochemical cells
A device which converts chemical energy into electrical energy or electrical energy into
chemical energy is called electrochemical cell. There are 2 types
1. The one which converts chemical energy into electrical energy is called galvanic cell.
2. The one which converts electrical energy into chemical energy is called electrolytic
cell.
An electrochemical cell consists of two electrodes. When the electrodes are connected by a
metallic wire, an electric current flow as a result of a spontaneous redox reaction. Each
electrode usually consists of a metal in contact with a solution of its own ions. Since a cell is
a combination of two electrodes, each electrode is referred to as a single electrode or a half
cell.
Single electrode potential(E)
When a metal is in contact with a solution of its own ions, the potential developed at the
interface between the metal and the solution is called single electrode potential.
Standard electrode potential(E0)
The potential developed when the electrode is in contact with a solution of unit concentration
at 298K. If the electrode contains gas then its pressure is one atmosphere. It is denoted by E◦.
Sign conventions
The electrode potential of an electrode is positive, if the electrode reaction is reduction when
coupled with the standard hydrogen electrode and electrode potential is negative if the
electrode reaction is oxidation when coupled with the standard hydrogen electrode.
Example
When copper electrode is combined with standard hydrogen electrode, copper electrode acts
as cathode and under goes reduction and hydrogen electrode acts as anode.
H2 2H+ + 2e- (oxidation)
Cu+2 + 2e- Cu (reduction)
Hence electrode potential of copper is assigned a positive sign. Its standard electrode
potential is 0.34V.

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When zinc is coupled with standard hydrogen electrode, zinc electrode acts as the anode
and undergoes oxidation and hydrogen electrode acts as the cathode.
Zn Zn+2 +2e-
2H+ + 2e- H2
Hence the electrode potential of zinc is negative. It is -0.76V.
Cell notation
If two electrodes are combined to form a cell, then the cell is represented by writing the
electrode conventions side by side with anode (negative electrode) on the left and the cathode
(positive electrode) on the right. The two electrode representations are separated by a double
line. The double line represents the presence of a salt bridge. Hence the cell can be
represented as:
M1|M1+n(C1)||M2+n(C2)|M2
Eg: Daniell cell can be represented as represented as follows:
Zn|Zn+2(1M)||Cu+2(1M)|Cu
Cell potential or EMF of a cell
It is the potential difference between two half cells in an electrochemical cell, which causes
the flow of current from one electrode (higher potential) to the other (lower potential).
It is denoted by Ecell.
Cell potential is calculated using the formula
Ecell = ER.H.E – EL.H.E
Ecell = Ecathode - Eanode
By knowing the electrode potentials of the electrodes constituting the cell, the cell potential
can be calculated.
Types of electrodes
Some of the important types of electrodes are grouped into the following types.
i) Metal –Metal ion electrode: where a metal is in contact with its ionic solution.
Eg: Cu+2|Cu, Zn+2|Zn, Ag+|Ag
ii) Metal- metal salt ion electrode (metal- insoluble salt electrode): where a metal is in
contact with its insoluble salt which is in contact with a solution containing the anion of the
salt.
Eg; Calomel electrode.
iii) Gas electrode: In this an inert metal such as platinum is in contact with gas molecules and
also with the ionic solution of the same gas molecule.

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Eg: Standard Hydrogen electrode (SHE).

iv) Amalgam electrode: where metal-amalgam is in contact with a solution containing its own
metal ions.
Eg: Lead- amalgam electrode (Pb- Hg|Pb+2)
v) Oxidation- reduction electrode: An oxidation-reduction electrode is the one in which the
electrode potential arises from the presence of oxidized and reduced forms of the same metal
substance in solution. The potential developed is picked up by an inert metal like platinum.
Eg: Pt |Fe+2, Fe+3
vi) Ion selective electrode (Membrane electrode): This electrode is more selective towards a
particular type of ion, in a mixture of ions and used to measure concentration of that
particular ion.
Eg; Glass electrode.
Ion Selective Electrodes
Ion selective electrodes are the electrodes that can interact more selectively with a particular
ion in a mixture of ions neglecting the other ions. The potential developed by an ion-selective
electrode depends only on the concentration of species or ions of interest. For e.g., Glass
electrode is H+ ion selective.
The electrodes consist of a membrane which is capable of exchanging the specific ions with
the solution with which it is in contact. Ion selective electrodes are also called membrane
electrodes.
Construction & working of Glass Electrode (Ion selective electrode)
A glass electrode consists of a long glass tube with a thin-walled bulb at one end. The Glass
is made of silicate glass containing SiO 2 , Na2O, CaO of high electrical conductance & low
melting point. The bulb contains 0.1M HCl & Silver - silver chloride electrode (Internal
reference electrode) is immersed into the solution & connected by a platinum wire for
external contact. The electrode is represented as Ag / AgCl(s) / 0.1M HCl / glass.

Glass

Ag- AgCl
0.1 M HCl
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If a thin-walled glass bulb containing an acid is dipped in a solution(analyte), a potential is

developed across the glass membrane. The potential difference E b at the interface is referred
to boundary potential, given by, Eb= E2 – E1

E1 = Potential of inner membrane , E2 = Potential of outer membrane

Eb = 0.0591 log C2
n C1
Since the concentration C1 of solution inside the glass bulb is constant
Eb = 0.0591 log C2 + L,

Where L = - 0.0591 log C1, here n=1 for H+ ion at 298K

Since C2 = [H+], the equation is represented as
Eb = L + 0.0591 log [H+]

Eb = L - 0.0591pH , Since pH = - log [H+]

The Potential of glass electrode (EG) is sum of three potentials

 Boundary potential (Eb)
 Potential of Ag/AgCl electrode
 Asymmetry potential (Easy)
Asymmetric potential is the potential that exists across the glass membrane even when the
concentration of external solution is equal to internal solution (C 1 = C2). This potential arises
due to some difference in thickness of the inner and outer surface or curvature of the glass
membrane. It varies with time and from one electrode to another electrode.

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Therefore, Glass Electrode potential EG = Eb+ EAg/AgCl + Easy

= L - 0.0591pH + EAg/AgCl + Easy

EG = L1 - 0.0591 pH where L1 = L+ EAg/AgCl + Easy

The above equation for potential of glass electrode is used to measure the pH of a solution.
Determination of pH using Glass Electrode
To determine the pH of a given solution the glass electrode is dipped in a solution whose pH
need to be determined. It is combined with a saturated calomel electrode which is a reference
electrode.

The emf of the so formed cell is determined potentiometrically.

Ecell = EG - Ecal
Ecell = L1 – 0.0591pH -Ecal

L1 value is determined by dipping the glass electrode in a solution of known pH and

measuring the emf of the cell formed when combined with a calomel electrode.

Reference Electrodes
Reference electrodes are the electrodes whose potentials are known and with reference to
those, the electrode potentials of other electrodes are measured.
Eg: Standard hydrogen electrode is the primary reference electrode as the electrode potentials
of other electrodes are assigned with respect to it.

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Because of the difficulties involved in the use of standard hydrogen electrode as primary
reference electrode some other electrodes of constant electrode potential, referred to as
secondary reference electrodes are employed as reference electrodes.
Two such electrodes which are in common use are calomel electrode and silver-silver
chloride electrode.
Calomel Electrode
The calomel electrode consists of mercury, mercurous chloride (Hg 2Cl2) and a solution of
KCl. Mercury is placed at the bottom of a glass tube. Mercury is covered by a paste of
mercurous chloride (calomel) with mercury and potassium chloride solution. A solution of
KCl is introduced above the paste through the side tube. A platinum wire sealed into a glass
tube is dipped into mercury and used to provide the external electrical contact. The
concentration of KCl solution used is either decinormal, normal or saturated.
Correspondingly the electrode is known as decinormal, normal or saturated calomel electrode
respectively.
The calomel electrode is represented as Hg| Hg2Cl2| Cl-

Depending upon the nature of the other electrode of the cell, the calomel electrode can act as
anode or cathode.
When it acts as anode the electrode reaction is
2Hg Hg2+2 + 2e-
Hg2+2 +2Cl- Hg2Cl2
2Hg +2Cl- Hg2Cl2 +2e-

When it acts as cathode, the electrode reaction is

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Hg2+2 + 2e- 2Hg

Hg2Cl2 Hg2+2 +2Cl-
Hg2Cl2 +2e- 2Hg + 2Cl-
The net electrode reaction is
Hg2Cl2 +2e- 2Hg + 2Cl-

The electrode potential depends on the concentration of the chloride ions.

At 298K, the electrode potentials are as follows
0.1N KCl electrode (0.334V) and Saturated KCl electrode (0.2422V)
Applications:
 It is used as a secondary reference electrode in the measurement of single electrode
potential.
 It is the most commonly used reference electrode for potential measurement.

Measurement of single electrode potential using secondary reference electrode (calomel

electrode)
The test electrode (eg: Zn|Zn+2) is coupled with a secondary reference electrode for example
saturated calomel electrode. It is represented as Zn|Zn+2||Cl-|Hg2Cl2|Hg
The emf of the cell is determined experimentally by potentiometric method then
Ecell = Ecathode – Eanode
Ecell = Ecal – EZn
Ecell = 0.2422 – EZn ie EZn = 0.2422 – Ecell

Concentration Cells

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Galvanic cells in which both the anode and the cathode are made up of the same element
(metal or non-metal) in contact with the solutions of the same electrolyte, but emf arises due
to difference in concentrations of electrolyte are referred to as concentration cells.
Eg: Concentration cell consisting of two half cells. Both the electrodes are made up of copper
metal but dipped in copper sulphate solutions of different concentrations. It is represented as
Cu|Cu+2(C1)||Cu+2(C2)|Cu
Where C1and C2 are the molar concentrations of the Cu+2 ions in the two half cells.
By convention left hand electrode is the anode and the right-hand electrode is the cathode.
The half-cell reactions are
Cu Cu+2(C1) + 2e- (Anode reaction)
Cu+2(C2) + 2e- Cu (Cathode reaction)
Adding the two half-cell reactions, the net cell reaction is
Cu+2(C2) Cu+2(C1)
The potential of the cell is Ecell = ER -EL

Where E◦ is the standard reduction potential of the species in the concentration cell. On
simplifying

C
Ecell = 0.0591 log 2 at 25oC
n C1

Ecell is positive if C2>C1

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In a concentration cell the electrode with lower electrolyte concentration acts as the anode
and the one with higher electrolyte concentration acts as the cathode.
Analytical Techniques
Analytical chemistry methods refer to techniques used for the detection, identification,
characterization, and quantification of chemical [Link] identifies analytes,
while quantitative analysis determines the numerical amount or concentration. Several
Instruments and sensors are being used for analysis as these methods are faster, accurate and
require a minimum quantity for analysis. Instrumental methods such as conductometry and
potentiometry are some examples of these methods.
CONDUCTOMETRY
Principle/ Theory
Conductometric titrations are the titrations in which amount of the analyte present in the
given solution is measured by the change in conductance. The principle underlying in
conductometry is the measurement of replacement of ions of a particular conductivity by ions
of different conductivity during a chemical reaction. Conductivity electrodes or sensors are
used to determine the end point in acid base titrations. Neutralization point is determined by
observing the change in specific conductance of the solution. Specific conductance(K) is the

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conductance of a solution present between 2 parallel electrodes of area 1cm 2 which are kept
1cm apart. Here R is the resistance.

The specific conductance of an electrolytic solution at any temperature depends on ions

present and hence varies with ionic concentration. The measurement of conductance is used
to determine the equivalence point in acid base titrations. In conductometric titration, there is
a sudden change in conductance of solution at equivalence point. Hence equivalence point is
determined by plotting a graph of conductance versus volume. Therefore, concentration of
the analyte in the solution can be calculated.
Instrumentation
Conductometer consists of 2 platinum electrodes and a conductance measuring device. The 2
electrodes have unit area of cross section and are placed unit distance apart. The solution to
be estimated is taken in a beaker. The system responds readily to changes in concentration of
analyte.

Advantages
 Mixture of acids can be titrated accurately.
 Accurate results are obtained in dilute as well as more concentrated solutions.
 The method can be employed for colored solutions also.

APPLICATION:
Estimation of Weak Acid
Titration of weak acid with a strong base: (CH3COOH Vs. NaOH)
The conductance of weak acid, acetic acid is initially low, due to poor dissociation. When a
strong base is added, the salt is formed, gets ionized and conductance increases slowly. After

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the complete neutralization, further addition of base NaOH introduces more and more Na +
and OH- ions into the solution, conductance again increases rapidly. When conductance of the
solution is plotted against volume of base added, two straight lines are obtained. The point of
intersection corresponds to the volume of base required to neutralize weak acid.

CH3COOH + NaOH → CH3COONa + H2O

The plot of conductance versus volume of strong base is as follows.

Procedure
Fill the microburrete with standard NaOH solution. Pipette out the given weak acid into clean
100 cm3 beaker. Immerse the conductivity cell connected to conductivity meter in acid
(CH3COOH) given. Add 0.5 cm3of the NaOH solution from the burette. Stir the solution
gently and measure the conductance. Continue the measurement of conductance after each
addition of 0.5 cm3 of NaOH solution. The titration should be continued till the slow increase
in conductance changes to sudden increases near equivalence point; and at least 5-6 readings
should be taken after that. Plot a graph of conductance on y- axis versus volume of NaOH on
x -axis. The volume corresponding intersection of two lines is the neutralization point of
Acetic acid.

POTENTIOMETRY
Principle
In potentiometric titrations, concentrations of the solutions can be calculated by measuring
the emf between two electrodes dipped in the analyte solution.
The potential of an electrode is given by Nernst equation,

i.e. The potential of an electrode depends on concentration of ion to which it is reversible.

This method can be used in the determination of end points of acid-base titrations, red-ox

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titrations etc. When a known volume of analyte is titrated with a standard solution,
neutralization or red-ox reaction takes place. During the course of titration, concentration of
product will be continuously altered. If a metal electrode, reversible with respect to
corresponding ions is placed in the solution, the potential will vary throughout the titration,
which can be determined using a suitable device. Initially, the change in potential is very
small. At the equivalence point, when the amount of titrant added is equivalent to the amount
of analyte present, there will be a sharp rise in potential. Beyond the equivalence point, there
will be no significant change in potential. By plotting a graph of change in potential against
the volume of titrant added, the equivalence point can be determined.
Instrumentation
Potentiometer consists of a reference electrode, an indicator electrode, and a potential
measuring device. The indicator electrode responds to the changes in concentration of
analyte. A reference electrode like saturated calomel electrode is also used. A known volume
of analyte is taken in the beaker and its potential is determined. The titrant is added in
increments of 0.5 ml and emf is measured each time. At equivalence point, emf increases
rapidly. At this point, titrant is added in small increments of 0.5ml. a few readings are taken
beyond the end point. Thus, the changes in potential at different volumes of titrant are
recorded.

ADVANTAGES:

 Potentiometric titrations can be carried out in colored solutions where indicators

cannot be used.

 By potentiometry, it is possible to determine the end point in titrations of redox,

precipitation and acid-base titrations.

CEC DEPARTMENT OF CHEMISTRY 2022 SCHEME

Chemistry For CSE Stream 22

APPLICATION:

Estimation of Iron (Fe) using acidified Potassium dichromate solution

Potentiometry can be used to determine the end point of a redox titrations by measuring the
change in potential during titration using a platinum-calomel electrode combination.
The titrations involving Mohr's salt solution and Potassium dichromate solution can be done
by Potentiometry.
 The platinum electrode is used as an indicator electrode and coupled with a calomel
electrode (reference electrode) and dipped in a solution of known volume of analyte
(Mohr's salt solution) and connected to potentiometer and emf is measured.
 The titrant (Potassium dichromate) of known concentration is added in increments of
0.5ml from burette to the analyte solution and emf is measured each time after stirring
the solution.
 FAS reacts with K2Cr2O7 under acidic conditions, the redox electrode potential is set
up at indicator electrode. Pt/Fe2+,Fe3+.
 The electrode potential of the redox electrode is given by Nernst equation

 The electrode potential depends upon concentration of Fe2+ and Fe3+,

 As the titration proceeds Fe3+ increases and Fe2+decreases and redox electrode
potential increases and emf of the cell goes on increasing and steep rise is seen at
equivalence point.
 At equivalence point all the Fe2+is converted to Fe3+ions and redox potential of
Pt/Fe2+,Fe3+ stops and further addition of dichromate new redox potential comes into
existence Pt/Cr6+,Cr3+ because the solution contains Cr3+ions produced due to
reduction of dichromate by Fe2+ ions. This redox electrode Pt/Cr6+,Cr3+ has higher
potential than Pt/Fe2+,Fe3+.
 Plot a graph of ΔE/ ΔV versus volume of K2Cr2O7 gives the equivalent point.

CEC DEPARTMENT OF CHEMISTRY 2022 SCHEME

Chemistry For CSE Stream 23

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Question Bank on Corrosion, Electrode System & Analytical techniques

1. What is corrosion. Explain the electrochemical theory of corrosion taking iron as
an example.
2. Define cathodic protection. Explain the sacrificial anode technique for prevention of
corrosion.
3. What is cathodic protection? Describe sacrificial anode technique and mention the
advantages and disadvantages.
4. Explain differential aeration corrosion with suitable examples.
5. Discuss the following types of corrosion.
a) Differential metal b) Differential aeration Corrosion
6. What is corrosion? Explain the rusting of iron based on electrochemical theory.
7. Describe galvanising and its applications.
8. What is anodizing? Explain anodizing of aluminium and its applications.

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Chemistry For CSE Stream 24

9. What are reference electrodes? Explain construction, working and application of

calomel electrode.
10. What is ion selective electrodes? Discuss construction, working and application of
glass electrode.

11. Write a note on type of electrodes.

12. Explain the theory and instrumentation of Potentiometry
13. Explain the theory and instrumentation of Conductometry
14. Explain the application of Conductometry in estimation of weak acid.
15. Explain the application of Potentiometry in estimation of Fe.
16. What is concentration cell? Explain the construction and working of concentration cell.
17. What is ion selective electrodes? Explain the determination of pH of a solution using
glass electrode.

Prashantha Somayaji
Assistant Professor
Department pf Chemistry
CEC, Benjanapadavu

CEC DEPARTMENT OF CHEMISTRY 2022 SCHEME