Corrosion and Electrode System

Vidya Vikas Institute of Engineering & Technology

Department of Chemistry (22 Scheme)
Sub Code: BCHES102/202

MODULE 3: CORROSION AND ELECTRODE SYSTEM 08 Hours

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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. ss
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.
Self-learning: IR and UV-Visible spectroscopy.
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Introduction
A wide variety of metals are used in our daily life. These metals have a
tendency to get deteriorated or tarnished by the influence of environment to which
they are exposed. The best example is the rusting of iron. However few metals like
Aluminium, Chromium, and Nickel etc. may get passivated or tarnished gradually due
to the surface layer oxidation of these metals in the presence of atmospheric oxygen
or air. Thus when metals are exposed to air, water or soil, they suffer chemical or
electrochemical attack which in chemical terminology known as corrosion.

Q1: Define Corrosion. Explain the types of Corrosion.

Corrosion is defined as the destruction or deterioration of metals by the surrounding

environment through chemical and electrochemical changes.

Types of corrosion:
There are two types of corrosion:
1. Dry or chemical corrosion: It is also known as direct chemical corrosion.
This mainly occurs through the direct chemical action of environment in the
dry state.
2. Wet or Electrochemical corrosion: It is also called indirect corrosion or
immersed corrosion. This takes place mostly under wet or moist condition
through the formation of short circuited Galvanic cells.

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Q2. Explain the electrochemical theory of corrosion by taking rusting of iron as

an example

Electrochemical theory of corrosion: When a metal, such as iron, is exposed to the

environment, according to electrochemical theory; Anodic and cathodic areas are
formed resulting in minute galvanic cells. Oxidation (corrosion) takes place at the
anodic area and electrons are liberated. The electrons released at the anodic area
migrate to the cathodic area and reduction takes place.
Step I: Reaction at anodic area
Metal Fe dissolves to give Fe+2 ions and electrons
Fe → Fe+2 + 2e- (oxidation reaction)

Step II: Reaction at cathodic area

Electrons released at the anodic area are conducted to the cathode and are
responsible for various cathodic reactions.
 In the presence of oxygen: oxygen in the environment dissolves in the
moisture
a) In acidic medium, H+ ions reduced to H2O
4H+ + 4e- + O2 → 2H2O
b) In neutral or slightly alkaline medium, dissolved oxygen reduced to
hydroxyl ions.
O2 + 2H2O + 4e- → 4OH-
Both the reactions involve absorption oxygen.
 In the absence of oxygen:
a. In acidic medium, H+ ions reduced to hydrogen gas
2H+ + 2e- → H2 ↑
b. In neutral or slightly basic medium, moisture reduced to
hydroxyl ions hydrogen gas
2H2O + 2e- → 2OH- + H2 ↑
Both the reactions involve evolution of hydrogen gas.

Step III: Formation of Fe(OH)2

Smaller Fe+2 ions diffuses faster than the larger OH- ions to the cathodic area through
the moisture and converted into Fe(OH)2. Hence, the corrosion current flows
between the anodic and cathodic areas through conducting media (metal).
Fe+2 + 2OH- → Fe(OH)2

Step IV: Formation of Rust

a) In the presence of excessive amount of oxygen, Fe(OH)2 is converted into
yellow rust (hydrated ferric oxide), Fe2O3.3H2O.
2Fe(OH)2 + ½O2 + H2O → Fe2O3.3H2O (yellow rust)

b) In the limited amount of DO, Fe(OH)2 is converted into black rust (ferrouos
ferric oxide), Fe3O4.3H2O.
3Fe(OH)2 + ½ O2 → Fe3O4.3H2O (black rust)

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Q3. Explain Galvanic (Differential metal) corrosion with an example.

Galvanic corrosion is caused when two

dissimilar metals are in contact with each
other in a corrosive environment. The metal
with lower electrode potential or more active
metal (higher in galvanic series) acts as anode
and undergoes corrosion. The metal with
higher electrode potential (lower in galvanic
series) acts as cathode and is free from
corrosion.
For example, if iron and copper are in contact with each other in presence of an
electrolyte then, iron which is higher in galvanic series (with lower electrode
potential) forms the anode and gets dissolved (corroded), while copper which is
lower in galvanic series (with higher electrochemical potential) acts as cathode and
is protected.
Corrosion reactions:
At anode: Metal Fe dissolves to give Fe+2 ions and electrons as Fe Fe 2+ + 2e-
At cathode:
• In acidic medium (and in the absence of oxygen), the corrosion occurs by the
hydrogen evolution process as 2H+ + 2e- H2↑
• In neutral or slightly alkaline medium (and in the presence of oxygen), oxygen
absorption occurs as H2O + ½ O2 + 2e- 2OH-

Q4: What is Differential aeration corrosion? Give example.

Corrosion of metals arising due to difference in

oxygen or air concentration on the metal surface
is known as differential aeration corrosion. The
part of the metal exposed to higher oxygen
concentration acts as cathodic region and part of
the metal exposed to lower oxygen concentration
acts as anodic region. Consequently, poorly
oxygenated (anode) region undergoes corrosion.

At the anode (less O2 concentration); M Mn+ + n e-

At the cathode (more O2 concentration); H2O + ½ O2 + 2e- 2OH-
Example: Waterline corrosion and pitting corrosion

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Q5. What is cathodic protection? Explain how the corrosion of a metal is

controlled by cathodic protection method.

Definition: Cathodic protection is defined as a method of protecting a metal or alloy

from corrosion by converting it completely into cathodic. Cathodic protection can be
achieved by the following methods: (i) Sacrificial anode method (ii) Impressed
current method.
Sacrificial anode method: In
this corrosion control method,
the metallic structure to be
protected is connected to a more
active metal with an insulated
copper wire. Thus, the metal structure acts as cathode and more active metal acts as
anode.
The more active metal itself gets corroded slowly; while the metal structure
(cathodic) is protected. The more active metal so-employed is called sacrificial anode.
The corroded sacrificial anode block is replaced by a fresh one, when consumed
completely. Metals commonly employed as sacrificial anodes are Mg, Zn, Al and their
alloys.
Important applications of sacrificial anodic method include protection of buried
pipelines, underground cables, marine structures, ship-hulls, water-tanks, etc.

Q6. What is metal coating? Write a note on Galvanization.

Deposition of a protective metal over the surface of a base metal is called metal
coating. Examples: Galvanization (anodic metal coating) and Tinning (cathodic metal
coating).
Galvanization: Galvanizing (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.
• The metal surface is first washed with organic solvents to remove oil and
grease deposits.
• Rust and other deposits are removed by washing with dilute sulphuric acid
(pickling).
• Finally the article is washed with water and air dried.
• The article is then dipped in a bath of molten zinc, maintained at 425-4300C
and covered with a flux of ammonium chloride to prevent the oxidation of
molten zinc.
• 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.

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Applications: Galvanization is most widely used for protection of iron from

atmospheric corrosion in the form of roofing sheets, wires, pipes, nails, bolts, screws,
buckets, tubes etc.
Disadvantages: Galvanized articles are not used for preparing and storing food
stuffs since zinc dissolves in dilute acids producing toxic compounds.

Uses: Because of non-toxic nature of tin, tinning is widely used for coating steel, Cu,
and brass sheets, used for manufacturing containers of storing foodstuffs, ghee, oils,
kerosene and packing food materials. Tinned-copper sheets are employed for making
cooking utensils and refrigeration equipments.

Q7. What is anodizing? Write a note on anodizing of aluminium.

Anodizing: It involves the electrolytic oxidation of metal surface to produce a tightly

adherent & durable oxide scale by passing electric current through an electrolyte to
impart more protection against corrosion. Anodized coating is generally produced on
non-ferrous metals like Al, Zn, Mg and their alloys.

Anodising of Aluminium is carried out by

electrolysis in a suitable acid electrolyte
(sulphuric or chromic acid) at moderate
temperature (35-40 0C) and moderate
current densities (10-20 mA cm-2).
Aluminium is made as anode and a plate of
lead or stainless steel is made as cathode.
The coating forms as a result of
progressive oxidation, starting at the
aluminum surface. When current is passed the oxygen liberated at anode combines
with it to form oxide which takes the form of thick film. The outer part of the oxide
film formed may be slightly porous and it is sealed by dipping in boiling water. This
treatment converts porous alumina at the surface of coating into its monohydrate
(Al2O3.H2O), which occupies more volume, there-by the pores are sealed.
Applications: It is used providing attractive, highly durable exteriors, roofs, ceilings,
floor, lobbies, escalators and staircases

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Q8. Write a short note on Corrosion penetration rate (CPR) ?

The corrosion penetration rate (CPR) is defined in three ways:
• 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 amount of corrosion loss per year in thickness.
• The speed at which corrosion spreads to the inner portions of a material.
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:
• 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: CPR = (k x W) / (D x A x T)

where k = a constant
W = total weight lost after exposure time
T = time taken for the loss of specimen
A = the surface area of the exposed metal
D = the metal density in g/cm³
The CPR is conveniently expressed in terms of either mils (0.001 inch) per year
(mpy) or millimeters per year (mmpy). K=534 to give CPR in mpy when surface area
of test specimen is in inch2 and K=87.6 for CPR in mmpy when surface area of test
specimen is in cm2. (Where, 1 mil = 0.001 inch, 1 inch2 = 6.45 cm2 and 1 cm2 = 0.155
inch2)
CPR in mpy CPR mmpy
K 534 87.6
W (wt loss) mg mg
(D)ρ g/ cm 3 g/ cm3
A inch2 cm2
t Hrs Hrs

Q9. What is an electrode? Explain the types of electrodes:

Electrode may be a metal or non-metal which is in contact with a solution of its own
ions.
Types:
1. Ion selective electrode (ISE): In this electrode, a suitable non- porous
membrane separates two solutions, containing similar ions of different
concentrations. The potential difference is developed on either side of the
membrane. Ex: Glass electrode, Fluoride electrode and Nitrate electrode.

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2. Gas electrode: This electrode consists of noble metal like Pt which is in contact
with a gas and a solution of ions of the gas. Since gases cannot conduct
electricity, an inert metal is used to make electrical contact. Ex: Hydrogen
electrode, Oxygen electrode and Chlorine electrode.
3. Metal-metal ion electrode: These are the electrodes where a metal is dipped in
a solution containing its own ion. Ex: Zn in ZnSO4 solution.
4. Metal-insoluble salt electrode: It consists of a metal and its sparingly soluble
salt in equilibrium. Ex: Calomel electrode, Silver-silver chloride electrode.

Q10. What is a Reference electrode? Give examples.

Any electrode of constant and reproducible potential, used to determine the potential
of other electrode is called reference electrode.
Ex: Standard hydrogen electrode—primary reference electrode
Calomel electrode—secondary reference electrode
Ag-AgCl electrode—secondary reference electrode

Q11. Give the construction, working and applications of calomel electrode.

Justify that it is a reversible electrode.

Construction: Calomel electrode is a metal-metal salt

ion electrode. A platinum wire is sealed inside a glass
tube dipped into mercury and used to provide the
external electrical circuit. Mercury is placed at the
bottom of glass tube. A paste of calomel (Hg2Cl2) and
mercury is placed over the pool of mercury. The
remaining part of the tube is filled either a saturated or
standard solution of potassium chloride. The calomel
electrode is represented as:

Representation: Hg (s) | Hg2Cl2 (s) | KCl (Sat)

Working principle: Calomel electrode can act as anode or cathode depending on the
nature of the other electrode of the cell. The electrode reactions are represented as
follows:
As anode: As cathode:
2Hg → Hg22+ + 2e- Hg2Cl2 → Hg22+ + 2Cl-
Hg22+ + 2Cl- → Hg2Cl2 Hg22+ + 2e- → 2Hg
2Hg + 2Cl- → Hg2Cl2 + 2e- Hg2Cl2 + 2e- → 2Hg + 2Cl-
The net reversible electrode reaction is
½ Hg2Cl2 + e- → Hg (l)+ Cl- (aq)
Electrode potential of calomel electrode is given by:
E = E0 – 0.0591 log [Cl-] at 298 K

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Advantages of calomel electrode (a secondary reference electrode):

➢ It is very simple in construction.
➢ The potential is reproducible and stable over a long period.
➢ Its electrode potential will not vary with temperature.
Applications of calomel electrode: It is the most commonly used as secondary
reference electrode for potential measurements of unknown electrodes.

Note: Since the calomel electrode is reversible with respect to chloride ion its
electrode potential depends on the concentration of KCl solution. At 298K, the
electrode potentials as follows:
KCl concentration 0.1N 1N Saturated
Electrode potential (V) 0.334 0.281 0.2422

Q12. What is an Ion selective electrode?

Ion-selective electrode is a membrane electrode which is selectively sensitive
to a specific ion in a mixture and potential developed at the electrode is a function of
concentration of that ion in the solution.
The electrode generally consists of a membrane which is capable of
exchanging the specific ions with the solution with which it is in contact. Therefore
these electrodes are also referred to as membrane electrodes. Example: Glass
electrode, Nitrate electrode, Fluoride electrode
Q13. Explain the construction and working principle of Glass electrode.
Mention its applications.

Construction: A glass electrode consists of a long glass

tube with a thin-walled glass bulb at one end. This glass
can specifically sense hydrogen ions up to a pH of about 9.
The bulb contains 0.1 M HCl and Ag/AgCl electrode (as
internal reference electrode) immersed into the solution
and connected by a platinum wire for electrical contact.
The electrode is represented as:

Ag | AgCl (s) | HCl (0.1M) | Glass

Working principle:
A glass bulb containing an acid is immersed in another solution, a potential is
developed across the glass membrane. The potential difference, EB at the interface
also referred to as the boundary potential is the result of difference in potential (E2 -
E1) developed across the gel layer of glass membrane between the two liquids.

The boundary potential, EB can be related to the difference in the hydrogen ion
concentration of the two solutions by the relation,

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Where C1 is the concentration of H+ ions of

acid solution inside the glass bulb and C2 is
the concentration of the acid solution into
which the glass bulb is dipped.

If the concentration C1 of the solution inside the glass bulb is constant, then the first
term on the R.H.S. of equation (2) is constant. Therefore

Substituting the value of R and F at 298K,

Where, L is a constant, which depends primarily on the pH of the solution taken in

the bulb and glass electrode assembly.
Since C2 = [H+] of the solution, Equation (4) is written as,

The membrane undergoes an ion exchange reaction; Na+ ions on the glass are
exchanged for H+ ions.
The boundary potential established due to the above reaction is mainly responsible
for the glass electrode potential EG is given by
EG= EB + EAg/AgCl ………….(5)
From equation (1), EB = 0 when C1 = C2. But in practice, it has been observed that
even when C1 = C2, a small potential is developed. This is called asymmetric potential
(Easy). Hence, Equation (5) can be written as
EG = EB + EAg/AgCl + Easy
EG = L - 0.0591 pH + EAg/AgCl + Easy
EG = EG0 - 0.0591 pH………….(6)
Where EG0 is a constant equal to L + EAg/AgCl + Easy

Application of Glass electrode: Glass electrode is used to determine the pH of an

unknown solution

Advantages of glass electrode:

• Glass electrode can be employed in the presence of strong oxidizing or
reducing substances and metal ions.
• It is not poisoned easily.

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• Accurate results are obtained between pH range 1-9. However, by using

special glass electrodes, pH 1-13 can be measured.
• It is simple to operate, can be used in portable instruments and therefore
extensively used in chemical, industrial, agricultural and biological
laboratories.
• Can be used in colored, turbid and colloidal solutions.
• Attain equilibrium immediately

Limitations of glass electrode:

1. The glass membrane though it is very thin, it offers high resistance. Therefore
ordinary potentiometers cannot be used; hence it requires sensitive electronic
potentiometers.
2. This electrode cannot be used for solutions for pH less than 1and greater than 9.
3. Fluoride ions attack the glass electrode easily.
4. In strongly acidic solutions of pH<1, the salt effect due to anions is observed.
5. It can be used up to a pH of 13 but being sensitive to Na+ ions above a pH of 9,
the linear relationship between glass electrode is altered. So an alkaline error is
introduced beyond a pH of 9, which should be taken into consideration

Q14. How do you determine the pH of the solution by using glass electrode?

The glass electrode is immersed in a solution of which pH is to be determined. It is

combined with a reference electrode such as a calomel electrode through a salt
bridge internally and externally through the potentiometer. The cell assembly is
represented as:

Hg | Hg2Cl2 (s) | KCl (sat.) || Solution of unknown pH | glass | HCl (0.1M) | AgCl | Ag(s)

The EMF of the above cell, Ecell is measured using an electronic potentiometer. Ecell
measured is the difference between potential of glass electrode EG and calomel
electrode (Ecal). The potential developed at the indicator glass electrode is higher
than the reference calomel electrode (EG > Ecal).
Hence, Ecell = Ecathode - Eanode
= EG -Ecal

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Ecell = [EG0 - 0.0591 pH] - Ecal (Since, EG = EG0 - 0.0591 pH)

G− −
0
0.0591pH =
E ECALECELL

0
E
G −E −
CALECELL
Therefore, pH =
0.0591
Where, E0G and Ecal are constants. By substituting Ecell value, pH of an unknown
solution is calculated.

Note: E0G value is evaluated by dipping the glass electrode in a solution of known PH
and measuring EMF of the cell formed when combined with calomel electrode.

Q15: What are concentration cells? Explain the construction, working principle
and applications of electrolyte concentration cell with an example.

A concentration cell is a galvanic cell which consists of two electrodes made up of

same material in contact with the same electrolyte, but of different concentrations.
Construction: Electrolyte
Concentration cell is a galvanic
cells consisting of both anode
and cathode made up of same
element (metal or nonmetal) in
contact with the solutions of the
same electrolyte of different
concentration.

A typical Copper concentration cell is shown in figure. It consists of two copper

electrodes, immersed in CuSO4 solutions of two different concentrations. These two
electrodes are externally connected by metallic wire and internally by a salt bridge.
The cell can be represented as,
Cu | Cu 2+ (C1) || Cu 2+ (C2) | Cu

Or Cu(s) / CuSO4 (C1) // CuSO4 (C2) / Cu(s) [where C2 > C1]

Working principle: By convention left hand electrode is the anode and

right handelectrode is cathode.

At anode Cu → Cu 2+ (C1) + 2e-

At cathode Cu 2+ (C2) + 2e- → Cu

----------------------------------
Net cell reaction Cu 2+ (C2) → Cu 2+ (C1)
----------------------------------
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 Corrosion and Electrode System

The net cell reaction is merely the change in concentration; as a result the
current flowsthrough the circuit.

The Nernst equation for the EMF of a concentration cell is given by the equation:

Applications: Used to determine the valence state of metal ions

Note:
1. 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.
2. If the two solutions are of the same concentrations, then, Ecell = 0
3. When C2/C1 > 1, log C2/C1 is positive & electrode potential is positive.
4. Higher the ratio of C2/C1, greater is the value of EMF of the cell. i.e., ECell
α C2/C1.

Q16. Explain the principal, Instrumentation and applications of

Conductometric Sensor (Conductometry).
Electrolyte conducts current by the migration of ions under the influence of an
electric field. Like metallic conductor, they obey Ohm’s law, E = IR
Ohm’s law states that the current “I” flowing through a conductor is directly
proportional to the applied potential, E and inversely proportional to the
resistance R of the conductor.
The reciprocal of the resistance is called the conductance.
The resistances of a homogeneous material of uniform cross section with an area
of “a” sp.cm. and length “l” cm is given by:
R = p 1/a,
Where, p is the specific resistance, The reciprocal of the specific resistance is
termed the specific conductance, Ƙ.
Specific conductance of an electrolyte solution I is the conductance of the solution
presentbetween two parallel electrodes of 1 cm2 area of cross section and 1 cm
apart.
Ƙ. = 1/R x 1/a
Where, 1/a is known as the cell constant and R is the resistance of the solution.

The specific conductance of an electrolyte solution at a given temperature is

related to the number of ions present, size of the ions and mobility of the ions. On
dilution of an electrolyte solution, its specific conductance decreases as the
number of ions per mL decreases. Conductance measurements are used to
determine the equivalence point in acid-base titrations. There is a sudden change

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in conductance of the solution after equivalence point. The equivalence point is

determined graphically by plotting conductance against the titre values.
Instrumentation: It consists of two
platinum electrodes (conductivity cell) each
of unit area of cross section placed at unit
distance apart. The electrodes are dipped in
the electrolyte solution taken in a beaker. It
is connected to a conductance measuring
device. The titrant is added from a burette
and the solution is stirred. The conductance
is measured after the addition of the titrant
at intervals of 0.5 / 1 ml.
Applications: Conductivity sensors and transmitters are used in many industries
such as food & beverage, chemicals, life sciences, pharma, water and power. The
sensor selection depends on the application and the conductivity range. To measure
low conductivities in pure and ultrapure water, choose conductive sensors.

Weak Acid + Strong Base (eg: CH3COOH Vs NaOH)

In this titration, the titrant is added from burette and the conductances are
measured during the course of titration. The measured conductance is a linear
function of the concentration of ions present, the conductance first decreases with
increase in the volume of titrant. After a certain point, it increases with the
addition of titrant. This point is known as equivalence point. The titration curve of
a weak acid like CH3COOH by a strong base NaOH showed the curved portion,
which is due to the following hydrolysis reaction,
CH3COOH + NaOH → CH3COONa + H2O
Consequently, the conductivity increases as the conducting power of sodium
acetate is more than that of the feebly ionized acetic acid. The titration curve is
shown in Fig.

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Q16. Explain the theory, Instrumentation and applications of Potentiometry.

Theory: The measurement of emf to determine the concentration of ionic species in

solution is referred to as potentiometry. The relation between electrode potential
of an electrode and metal ion concentration is given by Nernst equation:

Where E is the electrode potential that depends on the concentration of the Mn+ ion
to which it is reversible.
Instrumentation: Potentiometer consists of a reference electrode (saturated
calomel electrode), an indicator electrode (Platinum electrode) and a device for
measuring the potential. The indicator electrode responds rapidly to the changes in
the potential due to the concentration changes of the analyte. A known volume of the
analyte is taken in a beaker and its potential is determined by connecting the
assembly to a potentiometer. The titrant is added in increments of 0.5 ml and the
potential is measured each time. Near to the equivalence point, there is a sharp
increase in the potential. The end point is determined by plotting change in the
potential against the volume of titrant.

Example: The redox titration of ferrous ammonium sulphate against KMnO4 or

K2Cr2O7. The oxidizing agent is usually taken in the burette.
Applications: It finds applications in oxidation reduction titrations to estimate the
concentration of analyte in the sample solution. Potentiometric titration does not
depend on the colour change or redox indicators.

********************** END OF MODULE – 3 **********************

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