MODULE-3

CORROSION AND ELECTRODE SYSTEM

CORROSION CHEMISTRY
Definition of corrosion: Corrosion is defined as the destruction of metals or alloys through
chemical or electrochemical reactions by the surrounding environment.
Example: When iron is exposed to air in the presence of moisture, hydrated ferric oxide (rust) is
formed.

Electrochemical theory of corrosion taking iron as an example: According to

electrochemical theory, corrosion of metals takes place due to the formation of anodic and
cathodic regions on the same metal surface or when two different metals are in contact with each
other in the presence of a conducting medium.

O2
Fe2+ Fe2+ OH OH- -
H2O
Cathodic region
Anodic region
Electrons

Iron Metal

Reactions:
Reaction at anodic region: Oxidation of metal takes place at anode. Metal atoms are converted
into their ions liberating electrons. Consequently, metal undergo corrosion at the anodic region.
e.g. Fe  Fe2+ + 2 e-
Reactions at cathodic region: At the cathodic region reduction reaction takes place. Since the
metal cannot be reduced further, metal atoms at the cathodic region are unaffected by the
cathodic region. Some constituents of the corrosion medium take part in the cathodic reaction.

a) Liberation of hydrogen (in the absence of oxygen)

In acidic medium the reaction is
2 H+ + 2 e-  H2 
In neutral or alkaline medium, the reaction is
2 H2O + 2 e-  2 OH- + H2 
b) Absorption of oxygen (in the presence of oxygen)
In acidic medium, the reaction is
4 H+ + O2 + 4 e-  2 H2O
In neutral or alkaline medium, the reaction is
2 H2O + O2 + 4 e-  4 OH-
Overall reaction:
The electrons liberated at the anodic region migrate to the cathodic region constituting corrosion
current. The Fe2+ ions liberated at the anode and OH- ions formed at the cathode diffuse towards
each other. Since smaller Fe2+ ions diffuse more rapidly than OH- ions, their combination occurs
more commonly near the cathodic region produces Fe(OH)2. Corrosion of metal continues as
long as both anodic and cathodic reactions takes place simultaneously.
Fe2+ + 2 OH-  Fe(OH)2 
2 Fe(OH)2 + 1/2 O2 + H2O  Fe2O3 . 3 H2O (yellow rust is formed in an oxidising environment)
3 Fe(OH)2 + 1/2 O2  Fe3O4 . 3 H2O (black rust is formed in presence of limited oxygen)

Types of corrosion:
1. Differential metal /Galvanic corrosion:

Zn metal Fe metal Fe metal Cu metal

Anode Cathode Anode Cathode

This type of corrosion occurs when two dissimilar metals are in contact with each other and are
exposed to a corrosive environment. The two metals differ in their electrode potentials. The
metal with lower electrode potential acts as anode and the other metal with higher electrode
potential acts as cathode.
The anodic metal undergoes oxidation and gets corroded. A reduction reaction occurs at the
cathodic metal. The cathodic metal does not undergo corrosion.
The reactions may be represented as follows:
At anode: M  Mn+ + n e-
At cathode: 2 H2O + O2 + 4 e-  4 OH-
Higher the potential difference between the anodic and cathodic metals, higher is the rate of
corrosion. Also on the ratio of anodic area to cathodic area, environmental factors, tendency of
metal to exhibit passivity.
Example: When iron is in contact with zinc, iron acts as cathode and zinc acts as anode because
zinc has lower electrode potential compared to iron. Therefore, zinc undergoes corrosion. On
the other hand, when iron is in contact with tin, iron acts as anode because iron has lower
electrode potential compared to tin. Hence iron undergoes corrosion.
Other examples:
1. Steel screws in copper sheet.
2. Steel screws with copper washer.
3. Bolt and nut made of different metals

2. Differential aeration corrosion:

This type of corrosion occurs when two different parts of the same metal are exposed to different
oxygen concentrations. (e.g. An iron rod partially dipped in water.) The part of the metal which
is exposed to less oxygen concentration acts as anode. The part which is exposed to more
oxygen concentration acts as cathode. The anodic region undergoes corrosion and the cathodic
region is unaffected.
The reactions may be represented as follows:
At anode: M  Mn+ + n e- (Oxidation of M)
At cathode: 2 H2O + O2 + 4 e  4 OH-
-
(Reduction of O2

Iron

More O2,
(Cathode)

Less O2, (Anode)

Wate
r

Other examples:
1. Part of the nail inside the wall undergoes corrosion.
2. When a dirt particle sits on a metal bar, the part under the dirt undergoes corrosion.
3. Partially filled iron tank undergoes corrosion inside water.

Pitting corrosion: This is an example of

differential aeration corrosion. When a small
dust particle gets deposited on a steel surface,
the region below the dust particle is exposed
to less oxygen compared to the remaining
part. As a result, the region below the dust
particle acts as anode undergoes corrosion and forms a pit. The remaining region of the
metal acts as cathode and is unaffected.
The reactions may be represented as follows:

At anode: M  Mn+ + n e-
At cathode: 2 H2O + O2 + 4 e-  4 OH-
Formation of a small anodic area and a large cathodic area results in intense corrosion below the
dust particle.

Water line corrosion: This is an example of differential aeration corrosion. When a steel tank is
partially filled with water for a long time, the inner portion of the tank below the water line is
exposed only to dissolved oxygen, whereas, the portion above the water line is exposed to more
oxygen. Thus the portion below the water line acts as anode and undergoes corrosion. The
upper portion acts as cathode and is unaffected.
 More
oxygen, Rust
((Cathode)

Less
Oxygen Water
(Anode)

A distinct brown line is formed just below the water line due to the deposition of rust.
The reactions may be represented as follows:
At anode: M  Mn+ + n e- (Oxidation of metal, M)
At cathode: 2 H2O + O2 + 4 e-  4 OH- (Reduction of oxygen)
Other example: Ships which remain partially immersed in sea water for a long time undergo
water line corrosion.

Corrosion control
METAL COATINGS
Metallic coatings are applied on a metal in order to protect metal from corrosion.
Galvanizing: Galvanizing is the process of coating a metal surface such as iron with zinc metal.
Galvanizing of iron is an example of anodic metal coating on the surface of a cathodic metal.
Process: Galvanization is carried out by hot dipping method. It involves the following steps
1. The metal surface is washed with organic solvents to remove organic matter on the surface.
2. Rust is removed by washing with dilute sulphuric acid.
3. Finally, the article is washed with water and air-dried.
4. The article is then dipped in a bath of molten zinc. (Molten zinc is 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.
Application: Galvanization of iron is carried out to produce roofing sheets, fencing wire,
buckets, bolts, nuts, pipes etc.
(Note: Even if the Zn coating falls off at some places, the base metal (Fe) does not get corroded
at those places. (This is because the base metal acts as cathode. In corrosion process, the
cathodic metal always remains unaffected.) And because of the formation of small cathodic area
and larger anodic area corrosion process will not be there.
(Note: Galvanized articles are not used for preparing and storing food because zinc dissolves in
dilute acids producing toxic zinc compounds).

Galvanization diagram
INORGANIC COATING
Anodizing (Anodizing of aluminum): When aluminum metal is made anodic in an electrolytic
bath with sulphuric acid or chromic acid as the electrolyte, a thin layer of aluminium oxide
(Al2O3) is formed on the surface. This process is called anodizing of aluminium or anodic
oxidation of aluminum.
Process: The article is subjected to decreasing and polishing and then made as anode. Chromic
acid electrolyte is maintained at about 350C and suitable voltage is maintained to get desired
thickness of the oxide film. After anodizing it is subjected to sealing which involves heating with
boiling water or steam. When anodized aluminium is exposed to a corrosive environment, the
Al2O3 layer on the surface acts as a protective coating. Hence corrosion is prevented.

Anode reaction: 2Al + 3H2O → Al2O3 + 6H+ +6e-

Cathode reaction: 6H+ + 6e- → 3H2
Net reaction: 2Al + 3H2O → Al2O3 + 3H2
Other metals such as Mg, Ti etc. can also be anodized.
(Note: On anodizing, Al2O3 is formed on the surface as a porous layer. The layer may be made
compact by sealing, which involves heating with boiling water or steam. During sealing, Al 2O3
is converted into Al2O3.H2O which occupies higher volume. Therefore, the pores are sealed.)
Applications: Metals such as Al, Mg, Ti etc. are anodized to control corrosion.

CATHODIC PROTECTION
Sacrificial anode method:

Electrical conductor

Steel pipe Cathode

Mg Block
(Anode)
In cathodic protection, the metal to be protected is completely converted into a cathode. Since
cathodes do not undergo corrosion, the metal is protected against corrosion, by connecting
auxiliary anode which is more active metal such as Al, Mg, or Zn.

In sacrificial anode method, the metal to be protected is electrically connected to a more active
metal. For example, when steel is to be protected, it may be connected to a block of Mg or Zn.
In such a situation, steel acts as cathode and is unaffected. Mg and Zn act as anode and undergo
sacrificial corrosion. When the sacrificial anode gets exhausted, it is replaced with new ones.
Other examples: Mg bars are fixed to the sides of ships to act as sacrificial anode.
Mg blocks are connected to buried pipe lines.
Mg blocks are connected to buried oil storage tank.

Corrosion Penetration Rate (CPR)

Corrosion Penetration Rate (CPR) is defined as the amount of corrosion lost per year in
thickness. Mathematically,
𝐾𝑊
CPR= 𝜌𝐴𝑡
The CPR is conveniently expressed in terms of either mils per year (mpy) or millimeters per year
(mm/yr)
Where, 1 mil =0.001 inch
CPR in mpy CPR mm/yr
K 534 87.6
W(wt loss) mg Mg
ρ g/cc g/cc
A inch2 cm2
t hrs Hrs

Problems:
1. A sheet of carbon steel one-meter-wide by three meters long has lost 40g to corrosion over the
past six months. Convert that mass loss to a penetration rate of the steel in mm units and mpy
units. What would be the corrosion rate? (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

𝐾𝑊
CPR= 𝜌𝐴𝑡
 87.6 𝑋 40 𝑋 1000𝑚𝑔
CPR= g = 3.466 X10-3 mm/yr
7.8 𝑋3x100X100 𝑐𝑚2 𝑋 6x30X24 hrs
cc
CPR= 0.003466mm/yr

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

1 sq mt (m2) = 1550 sq inch

𝐾𝑊 534 𝑋 40 𝑋 1000𝑚𝑔
CPR= CPR= g = 0.1363mpy
𝜌𝐴𝑡 7.8 𝑋3x1550 𝑖𝑛2 𝑋 6x30X24 hrs
cc

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
𝐾𝑊 𝐾𝑊
CPR= 𝜌𝐴𝑡 and t=𝜌𝐴𝑐𝑝𝑟

534𝑋2.6𝑋106 𝑚𝑔
t= 7.9 𝑔/𝑐𝑐𝑋10𝑖𝑛2 𝑋200𝑚𝑝𝑦 t= 87873.41hrs

87873.41
t= 365𝑋24 = 10.03𝑦𝑟𝑠

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

𝐾𝑊 534 𝑋 485 𝑋 1000𝑚𝑔

CPR= 𝜌𝐴𝑡 CPR= g
7.9 𝑋100 𝑖𝑛2 𝑋 365 X 24 hrs
cc
CPR=37.424mpy

Given CPR in mm/y

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

1 in2 = 6.45cm2
1 cm2= 0.155 in2

𝐾𝑊 87.6 𝑋 485 𝑋 1000𝑚𝑔

CPR= 𝜌𝐴𝑡 CPR= g =0.9518mm/y
7.9 𝑋100X6.45 𝑐𝑚2 𝑋 365X24 hrs
cc

ELECTRODE SYSTEM
TYPES OF ELECTRODES
1.METAL METAL ION ELECTRODE
Eg: Zn/Zn 2+, Cu/Cu2+
2.METAL METAL SALT ION ELECTRODE
Eg: Calomel Electrode(Hg/Hg2Cl2/Cl--)
Silver –Silver chloride electrode (Ag/AgCl/Cl--)
3. GAS ELECTRODE
Eg: Hydrogen Electrode (Pt/H2/H+)
4. OXIDATION REDUCTION ELECTRODE
Eg: Pt/Fe2+ /Fe3+
5. ION SELECTIVE ELECTRODE
Eg: Glass electrode
Reference Electrode:
Definition: Reference electrodes are the electrodes with reference to those, the electrode
potential of any electrode can be measured. They are of two types; Primary reference electrode
(eg: SHE) and secondary reference electrode.

SECONDARY REFERENCE ELECTRODES:

Secondary reference electrodes are the electrodes with reference to those, the electrode potential
of any electrode can be measured.
Examples: 1. Calomel electrode 2. Ag-AgCl electrode
Calomel electrode: It is a metal-metal salt ion electrode
It consists of mercury, mercurous chloride and a solution of KCl. Mercury is placed at the
bottom of a glass tube. A paste of mercury and mercurous chloride is placed above the mercury.
The space above the paste is filled with a KCl solution of known concentration. A platinum wire
is kept immersed into the mercury to obtain electrical contact.

Calomel electrode can be represented as, Hg| Hg2Cl2|Cl-.

The calomel electrode can acts as anode or cathode depending on the nature of the other
electrode of the cell.

When it acts as anode, the electrode reaction is,

2Hg Hg22+ + 2e-

Hg22+ + 2Cl- Hg2Cl2

2Hg + 2Cl- Hg2Cl2 + 2e-

When it acts as cathode, the electrode reaction is,

Hg22+ + 2e- 2Hg

Hg2Cl2 Hg22+ + 2Cl-

Hg2Cl2 + 2e- 2Hg + 2Cl-

The net cell reversible electrode reaction is,

Hg2Cl2(s) + 2e- 2Hg(l) + 2Cl-

Electrode potential, E  E0 
2.303 RT
nF
 
. log Cl 
2
 E  E0 
2.303 RT
F
 
. log Cl  , Where n=2

E  E 0  0.0591. log Cl    at 298K

Therefore, electrode potential of calomel electrode is depending upon the concentration of KCl.
For saturated KCl, the potential is +0.242V, for 1N and 0.1N KCl the values are 0.281V and
+0.334V respectively.
Applications:
1.It is used as secondary reference electrode in the measurement of single electrode potential
2. It is used as reference electrode in all potentiometer determinations
3. It is used as a secondary reference electrode in place of calomel electrode / glass electrode /
ion selective electrodes.
4. Used in determining whether the potential distribution is uniform or not in ship hulls and old
pipelines protected by cathodic protection.
5. As a portable reference electrode for measuring the different depths of oil rigs and platforms,
submerged oil pipelines etc. usually such probe is powered by Ni – Cd battery and can operate
up to a depth of 300-400m with precision of 1mv.
Ion selective electrode: Definition: “Ion selective electrode is one which selectively responds to
a specific ion in a mixture and the potential developed at the electrode is a function of the
concentration of that ion in the solution”

Glass electrode: A glass electrode is an ion selective electrode where potential depends upon the
pH of the medium.
The glass electrode consists of a glass bulb made up of special type of glass (22 % Na2O) which
has low melting point and relatively high electrical conductivity. The glass bulb is filled with a
solution of constant pH (0.1MHCl) and inserted with a Ag-AgCl electrode, which is the internal
reference electrode and also serves as the external electrical contact. The electrode dipped in a
solution containing H+ ions.
The electrode representation is Ag(s) |AgCl | 0.1M HCl| Glass

0.1 M
HCl

Ag-AgCl
electrode
H+ Ion
Solution
Glass
electrode
Working

The boundary potential is given by Nernst equation at membrane Eb = Ec – Ea

Therefore Eb = [E˚+0.0591 log C1] – [E˚+0.0591 log C2]
 Eb = 0.0591 log C1 – 0.0591 log C2
Eb = K + 0.0591 log [ C1] const. K= - 0.0591 log[C2]

Eb = K – 0.0591pH since C1=[ H+] and pH= - log [ H+]

Therefore EG = Eb + EAg/AgCl +Easym

EG = K – 0.0591pH + EAg/AgCl +Easy

EG= E˚G – 0.0591pH where E˚G = K+ EAg/AgCl +Easy

Determination of pH using glass electrode:

Principle: When a thin glass membrane is placed between two solutions of different pH values, a
potential difference arises across the membrane. The potential difference varies as the pH of
these solutions varies. In practice, pH of one of these solutions is kept constant and therefore the
electrode potential depends on pH of the other solution i.e experimental solution.

pH Meter

Glass
Calomel electrode
electrode

Solution of
unknown pH

Procedure: Glass electrode is immersed in the solution whose pH is to be determined. It is

combined with a reference electrode such as a calomel electrode (through a salt bridge= porous
disc). The cell assembly is represented as,
Hg(Ɩ)| Hg2Cl2|Cl-||Solution of unknown pH|Glass|0.1M HCl |AgCl |Ag(s)
The emf of the above cell, Ecell is measured using an electronic voltmeter with a pH meter.
The emf of the cell is given by
E cell=E Cathode- E anode
E cell = E˚G – 0.0591pH -ESCE
pH = E˚G – ESCE – Ecell
----------------------------------
0.0591
Advantages
1. This electrode can be used to determine PH in the range 0-9, with special type of glass even up
to 12 can be calculated.
2. It can be used even in the case of strong oxidizing agents.
3. The equilibrium is reached quickly.
4. It is simple to operate, hence extensively used in various laboratories.
Limitations
1. The glass membrane though it is very thin, it offers high resistance. Therefore ordinary
potentiometers cannot be used; hence it is necessary to use electronic potentiometers.
2. This electrode cannot be used to determine the PH above 12.

Concentration cells: A concentration cell is an electrochemical cell in which the electrodes and
the electrolyte solutions in both the half cells are composed of the same
element/substance/material, but only the concentrations of the two electrolyte solutions are
different.

Construction: A typical example of Zinc concentration cell is shown below.

e-

Salt bridge

+
- Zinc
Zinc
Anode Cathode

ZnSO4 C1 C2 ZnSO4
Solution Solution

It consists of two zinc electrodes are immersed in two different concentrations of ZnSO4
solutions. These two electrodes are externally connected by metallic wire and internally by a salt
bridge. The cell can be represented as,
Zn(s) |Zn2+ (C1) || Zn2+ (C2) | Zn(s)
By convention left hand electrode is the anode and right hand electrode is cathode.

Working:
At anode Zn Zn2+(C1) +2e
At cathode Zn2+(C2) + 2e Zn

Net cell reaction Zn2+(C2) Zn2+(C1)

The net cell reaction is merely the change in concentration as a result of current flow.

Emf of concentration cell:

We know that electrode potential depends upon the concentration of the electrolyte. By
convention, the potential of the cell is
Ecell = Ecathode - Eanode ………..1
 logC 2  logC1
0.0591 0.0591
Ecell= ………2
n n

Ecell 
0.0591 C 
log 2 at 298K
n C1  ………3

From equation (3) following conclusions may be drawn.

1. When the two solutions are of the same concentration, then log
C 2  and no electricity flows.
C1 
Hence, Ecell = 0
2. When C2/C1>1 ic C2>C1, log C2/C1 is positive & electrode potential is positive.
3. Higher the ratio of C2/C1, higher is the value of cell potential.
Numerical Problems:
1. Calculate the emf of copper concentration cell at 250C, the copper ions ratio in the cell is 10.
[Cu 2 ]cathode C 2
Given:   10
[Cu  2 ]anode C1
0.0591  C 2 
w.k.t E cell  log  ; at 298 K
n  C1 
0.0591
E cell  log( 10)
2
Ecell = 0.0296 V.

2. A concentration cell was constructed by immersing two silver electrode in 0.05M and 1M
AgNO3 solution. Write the cell representation, cell reactions and calculate the EMF of the cell.
Cell representation: Ag(s)AgNO3(0.05M)  AgNO3(1M)  Ag(s)
0.0591  C 2 
E cell  log 
n  C1 
At anode: Ag(0.05M) Ag+(0.05M) +e-
At cathode Ag+ (1M) + e- Ag (1M)

Net cell reaction Ag(0.05M) + Ag+ Ag+ (0.05M)+ Ag

0.0591  1 
Ecell  log
 0.05 
 
Ecell = 0.0768V

3. The spontaneous galvanic cell Tin/Tin ion(0.024M)//Tin ion(0.064M) /Tin develop an emf of
0.0126 V at 25OC, Calculate the Valency of Tin.
 0.0591  C 2 
E cell  log 
n  C1 
0.0591  C 2 
n log 
Ecell  C1 
0.0591  0.064 
n log 
0.0126  0.024 
n =2(Valency of tin)

ANALYTICAL TECHNIQUES
1. CONDUCTOMETRY
It is an electrochemical method of analysis used for the determination or measurement of the
electrical conductance of an electrolyte solution by means of a conductometer.
Conductometry means measuring the conductivity of an ionic solution
Conductance is ease with which current flows through the solution. It is reciprocal of resistance.
C=1/R (Unit is Ω-1 or mho or Siemens)
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 an inversely proportional to the resistance. I = V/ R
The resistance of the any conductor is directly proportional to the length and inversely
proportional to the area of cross section of the conductor. R α l/a
R = S (l/a) where S is specific resistance
Therefore 1/S = 1/R (l/a);
K = C (l/a), K = specific conductance, Specific conductance is also called
conductivity. It is the conductance of 1cm3 of solution.
It is defined as the conductance of the solution which is place between two electrodes of area
1cm2 and 1cm apart.
The conductance of the solution depends on mobility of ion, number of ion, charge of ion, size of
ion and temp.
Types of conductance:
Specific conductance (K) is conductance of the solution which are placed between two
electrodes of area 1cm2 and at 1cm apart
κ = 1/R (l/a) κ = 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

Weak acid v/s Strong base

CH3COOH against NaOH
CH3COOH + NaOH CH3COONa + H2O

The conductance of the acid will be initially low since acetic acid is a weak electrolyte. When
NaOH is added to the acid, the salt formed is highly ionized and the conductance increases. On
complete neutralization of the acid, further addition of base leads to increases in the number of
mobile OH- ions. Hence the conductance increases sharply. A plot of conductance against the
volume of base added is shown in the figure. The point of intersection of two curves gives the
endpoint.

Volume of NaOH Conductance

Advantages:
 Mixture of acid can be titrated
 Indicators are not used
 Very weak acids can be titrated
 Can be used with colored solution.

2. POTENTIOMETRY
A method of determination of the concentration of a solution by measuring EMF using
potentiometer is called Potentiometry.
Principle: Redox titrations can be carried out potentiometrically using platinum and calomel
electrode combination in a manner similar to acid-base neutralizations.
For the reaction; Reduced form  Oxidised form  n electrons
The potential is given by Nernst equation
0.0591 [Oxidised form]
E  Eo  log
n [Reduced form]
0.0591 [Fe3]
E  Eo  log
n [Fe2]

Instrumentation
Platinum electrode: An indicator electrode, potential of which changes with change
in concentration metal ions of the solution.
Calomel electrode: a reference electrode and potential of which is fixed.
Beaker: Test solution.
Burette: Standard K2Cr2O7 solution.
Procedure: Pipette out 25.0 cm3 of ferrous ammonium sulphate solution into a clean
beaker. Add a test tube of dilute sulphuric acid. Immerse the platinum-calomel
electrode assembly into the beaker containing the test solution. Connect the
electrodes to the potentiometer. Note down the emf of the cell before the addition of
K2Cr2O7. Now add 0.5 ml of K2Cr2O7 from the semi micro burette. Allow the solution
to mix well and measure the potential. Continue the procedure till a sudden rise in
∆𝐸
emf of the cell is observed. Take about 4-5 more readings. Plot a graph of ∆𝑉 vs volume
of K2Cr2O7 and calculate the volume of K2Cr2O7 consumed by FAS from the graph.

Vol.of K2Cr2O7 Emf E ∆V ∆E ∆E/∆V

(V) ml (mv) (V2V1) ml (E2-E1) (mv/ml)

Application of potentiometry: The method is used for different types of titrations

like,
1. Acid base titrations
2. Diazotization titrations
3. Redox titrations
4. Complexometric titrations
5. Precipitation titration
Advantages of Potentiometric titration
1. The method is inexpensive.
2. This method provides accurate results with minimal chances of errors.
3. Can be used for colored, turbid or fluorescent analyte solution.
4. Can be used in the titration of mixture of acids or mixture of bases.