MODULE-3 22CHES12

JSS ACADEMY OF TECHNICAL EDUCATION, BENGALURU

JSS Campus, Uttarahalli-Kengeri Main Road, Bengaluru-560060.
Department of Chemistry
Applied Chemistry for Computer Science & Engineering stream (22CHES12/22)

Academic Year: 2022-23 Faculty: Dr. Roopashree B

Course Outcome:
Student will be able to
Utilize the principles of electrochemistry for electrochemical cells, analytical techniques and
for corrosion and its prevention.
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.

Introduction:
Electrochemistry is the branch of chemistry, which deals with the study of inter conversion of
electrical energy and chemical energy.
Electrochemical cells
The devices which convert chemical energy into electrical energy and electrical energy into
chemical energy are called electrochemical cells. Cells consist of two electrodes immersed in
suitable electrolytes.
Classification of electrochemical cells
Electrochemical cells are classified as electrolytic cells and galvanic cells.

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Electrolytic cells
Electrolytic cell is a device which converts electrical energy supplied from the external
source into chemical energy.
Galvanic cells
A galvanic cell is a device in which the free energy of a physical or chemical process
is converted into electrical energy.
Reactions
The process of conversion of chemical energy into electrical energy is called electrochemical
reaction. Electricity is generated in a galvanic cell by the spontaneous reduction – oxidation
(redox) reaction taking place in a physically separated half cell. Half cell consists of a metal
dipped in suitable electrolyte. When two half cells are connected internally through a salt bridge
and externally through a voltmeter or a galvanometer, it forms a cell. The electrode at which
oxidation takes place is the anode and the electrode at which the reduction takes place is the
cathode.
Oxidation reaction involves loss of electrons. When a metal M loses electrons it is
oxidized to Mn+ ions. The oxidation reaction is written as:
M → Mn+ + ne-
Reduction reaction takes place at the cathode. Reduction is the gain of electrons,
Mn+ + ne- → M
Example:
A Daniel cell consists of a zinc rod dipped in the ZnSO4 solution and a copper rod dipped in
copper sulphate solution, connected by a metal wire.
Zinc being more electropositive undergoes oxidation.
Zn → Zn2+ + 2e- (1)
Electrons are left behind on the zinc rod and Zn2+ ions move into zinc sulphate solution.
At the copper half cell, Cu2+ ions from the CuSO4 solution gain electrons and are reduced to
Cu atoms.
Cu2+ + 2e- → Cu (2)
Reactions (1) and (2) occurring at each half cell are called half cell reactions.
When two half cell reactions are added we get a net cell reaction.
i.e., (1) + (2), Zn + Cu2+ → Zn2+ + Cu

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Notations and conventions

• Anode of a galvanic cell is ‘negative’ since oxidation takes place at the anode to give
metal ions and electrons. Metal ions go into solution leaving behind electrons on the
metal rod hence metal acquires a negative charge.
• The cathode of a galvanic cell is ‘positive’. At the cathode, metal ions in the solution
take up electrons from the metal rod and undergo reduction to give metal atoms. Metal
rod becomes electron deficient and acquires a positive charge.
• Representation of a galvanic cell
Anode | Electrolyte in which anode is placed ||Electrolyte in which cathode is placed |
cathode
The anode is always written on the left-hand side while the cathode is written on the
right-hand side. Single vertical lines indicate the interface or boundary between the
metal and solution. Double vertical line denotes the salt bridge. Arrow represents the
direction of flow of electrons.
Daniel cell is represented as

→
Zn | ZnSO4 (C1) || CuSO4 (C2) | Cu
Or
→
Zn | Zn2+ (C1) || Cu2+ (C2) |Cu
C1 and C2 are the concentrations of the electrolytes.
• Electrode potential
By international agreement, electrode potential always refers to the reduction potential of
the metal represented as E ֯Mn+/M and, under standard conditions, standard reduction
֯ n+/M
potential (SRP) is represented by E M
If oxidation potential of a metal is + X volts then its reduction potential is –X volts.
• Emf of a cell is given by
Ecell = Ecathode - EAnode
• Standard emf of the cell,
E ֯cell = E ֯cathode – E ֯Anode
Where E ֯cathode and E ֯Anode are the SRPs of cathode and anode respectively.
• Ecell is positive for the spontaneous cell reaction and the cell is a source of electrical
energy.
• Ecell is negative for a non – spontaneous cell reaction and therefore the cell is not a
source of electrical energy.
• In a galvanic cell, the metal with higher SRP is the cathode and the other with lower
SRP is the anode.

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Reference Electrodes
These are the electrodes of constant potential with which the electrode potential of other
metals can be compared. There are three main requirements for a satisfactory reference
electrode system.
These are (1) reversibility, (2) reproducibility, and (3) stability.
There are two types of reference electrodes.
(i) Primary reference electrode and (ii) Secondary reference electrode.
(i) Primary reference electrode
Standard hydrogen electrode is the primary reference electrode.
(ii) Secondary / Subsidiary reference electrodes.
These are the electrodes, whose potentials are measured on H2 scale and are used to
measure the electrode potential of other metals.
1. Calomel electrode
2. Silver – silver chloride electrode.

1. Calomel electrode
Calomel electrode is the most important electrode of all the secondary reference
electrodes. This is also called mercury- mercurous chloride electrode.
Construction:
It consists of a container made up of glass with two side tubes. One at the top is used to
fill KCl solution. The side tube is connected to the salt bridge. Mercury of high-grade purity is
placed at the bottom of the container over which a layer of paste of mercurous chloride
(Calomel) is added. Potassium chloride solution is filled from the opening. The electrical
connection with mercury is made by means of a platinum wire sealed in a glass tube. KCl
solution filled in the side tube is used for coupling with another half cell through the salt bridge.
Calomel electrode is represented as
Representation:
Hg | Hg2Cl2, KCl (aq)

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Working:
When the reaction involved is reduction,
+ –
2Hg (aq) +2e → 2Hg(l)
+ –
Hg2Cl2 (s) → 2Hg (aq)+2Cl
– –
Hg2Cl2 +2e → 2Hg(s) +2Cl
0.0591
Ecalomel = E 0 calomel − log k
n
– 2
Here, K = [Cl ]
0 –
Ecalomel = E – 0.0591 log [Cl ]
Therefore the electrode is reversible with respect to chloride ions. Hence the potential
developed by the calomel electrode depends on the concentration of Cl- ions. The
electrode potential decreases with an increase in the concentration of Cl- ions.
The potential of calomel electrode is measured with respect to SHE and, it depends on
the concentration of KCl solution used.
With 0.1 N KCl, potential developed by the calomel electrode is 0.334 V (Decinormal
calomel electrode)
With 1N KCl, potential developed by the calomel electrode is 0.280 V (Normal Calomel
electrode)
With saturated KCl, potential developed by the calomel electrode is 0.2422 V (Saturated
calomel electrode or SCE)
When the reaction involved is oxidation,
+ -
2Hg(l) → 2Hg (aq) +2e
+ -
2Hg (aq) + 2Cl (aq) → Hg2Cl2(s)
----------------------------------------------

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- -
2Hg(s) + 2Cl (aq) →Hg2Cl2(s)+ 2e
Advantages of calomel electrode are:
1. Simple in construction.
2. Electrode potential is reproducible.
3. Electrode has low temperature coefficient.
4. Used to measure the electrode potential of other metals and also used as reference
electrode to measure pH of the given solution.

Measurement of electrode potential using calomel electrode.

Electrode potential of a given electrode can be measured by taking calomel electrode
as a reference electrode. For ex., to measure the electrode potential of zinc, zinc half cell is
constructed by placing a zinc rod in zinc sulphate solution and it is coupled with saturated
calomel electrode (SCE). Emf of this cell is measured using a potentiometer. SCE is a
reference electrode of known potential, the potential of zinc electrode can be calculated as
follows.
Zn | ZnSO4(C1M)|| KCl (satd.) | Hg2Cl2| Hg

Working :
2+
At anode, Zn →Zn + 2e– -------(1)
– –
At cathode, Hg2Cl2 + 2e → 2Hg + 2Cl -------(2)
2+ –
Net cell reaction Zn + Hg2Cl2 → Zn + 2Hg + 2Cl
Ecell is measured using a potentiometer
Ecell = Ecathode – Eanode
= ESCE – Ezn2+ /zn
Ezn2+ /zn = ESCE - Ecell
ESCE = 0.2422 V
Therefore, EZn2+ /Zn = 0.2422 – Ecell
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Ion Selective Electrodes (ISE)

Ion selective electrodes are also called membrane electrodes or ion-sensitive electrodes.
These electrodes are fundamentally different from metal electrodes both in design and in
principle. All the ion selective electrodes make use of a kind of membrane which has selectivity
for certain specific ions. Hence, the potential developed by the ion selective electrodes is a
measure of the concentration of specific ions in the solutions.
Ion selective electrodes are the electrodes that respond to certain specific ions present in a
solution containing the mixture of ions and they develop potential due to the presence of these
specific ions by ignoring the presence of other ions in the solution.
Types of membrane employed in ion-selective electrodes are
(i) Solid state membranes
-
a) F selective electrode consists of a single crystal of LaF3 in contact with a mixture of 0.1
M solution of sodium fluoride doped with Eu(II) fluoride.
b) Electrodes selective to other halides, sulphide, cyanide, silver, lead, copper, consist of
membrane fabricated with pure or doped Ag2S.
(ii) Liquid state membranes
a) Liquid ion exchangers selective to cations or anions.
b) Monocyclic crown ethers in a hydrocarbon solvent.
c) A calcium-sensitive electrode consists of calcium dialkyl phosphoric acid.
iii) Heterogeneous membrane
Silicone rubber or a graphite matrix incorporating insoluble salts or metal complexes
capable of responding to ions like sulphates, nitrates & phosphates.
iv) Gas sensing electrodes
Contain a thin gas permeable membrane with a suitable electrolyte which interacts with
a specific gas.
v) Glass membrane
Widely used glass membrane is corning 015 glass with 22% Na2O, 6% CaO, 72% SiO2.
This shows excellent specificity towards hydrogen ions up to pH 9.
Components of Ion- selective Electrode
The Components of Ion- selective Electrodes comprise of a Membrane in contact with
the internal standard solution. Ion selective electrode also consists of a reference electrode in
contact with the internal standard solution called the internal reference electrode.
Principle
A membrane separates two solutions and the potential developed across the membrane
is related to the activities of the ions of interest in the standard solution and the analyte solution.
Schematic representation of ISE

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C1 and C2 are concentrations of the analyte and internal standard solution respectively
EISE = EM + Eref

EM is the potential developed across the membrane.

Eref is the potential developed by the internal reference electrode.
The Potential difference across the membrane,

The potential developed by the ion-selective electrode is a function of the concentration

of ions of interest present in the analyte solution.
Applications of Ion selective electrodes
1. Determination of concentrations of cations such as K+, Ca2+, Mg2+, Ag+, Cd2+,
Pb2+, Cu2+.
2. Determination of total hardness of water.
3. Determination of pH of the solution
4. Determination of concentration of anions such as NO3-, CN-, F-, and S2-
5. In testing blood gases and blood electrolytes.
6. Potentiometric determination of F- in drinking water.
Glass Electrode
(i) It is a hydrogen ion responsive electrode.
(ii) Potential developed by glass electrode is a function of hydrogen ion concentration. This
observation was made by Haber & Klemenslauriz (1909).
(iii) It is made up of glass membrane of high electrical conductivity. The composition of the
glass membrane is approximately 22% Na2O, 6% CaO, & 72% SiO2.
(iv) This membrane shows excellent specificity towards hydrogen ions up to a pH of about
9.0

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(v) Glass membrane involves an ion exchange reaction between sodium ions in the
interstices of the glass lattice and hydrogen ions from the solution. The ion exchange
reaction can be written as
+ + – + + –
H (aq) + Na Gl (Glass) Na (aq) + H Gl (Glass)
Construction
Glass electrode consists of a glass bulb of pH-sensitive glass membrane sealed onto one end of
the glass tube. The bulb is filled with 0.1 M HCl solution into which the Ag/AgCl electrode is
immersed.

Glass electrode is represented as

Ag | AgCl | HCl(0.1 M) |Glass
Working of Glass Electrode
The Two surfaces of Glass electrode must be hydrated before it is used.
The potential developed when a glass electrode is in contact with analyte solutions is

i) The potential developed by Ag – AgCl electrode in contact with 0.1M HCl Solution
(Eref)
ii) Potential developed by the glass membrane is EM or Eb is given by,
EM = E1 ~ E2
Where E1 and E2 are the potentials appearing at the two surfaces of the glass membrane
as a consequence of ion-exchange reaction between Na+ of glass and H+ in the solution.
EM = E1 – E2 = 0.0591 log C1 - 0.0591 log C2
EM = L + 0.0591 log C1
C2 is a constant = concentration of H+ ions in the internal standard solution.
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L = Constant = -0.0591 log C2

The potential of Glass electrode is given by
Eg = EM+ Eref + Easym
Asymetric potential: When identical solutions and reference electrodes are placed on the two
sides of the glass membrane i.e. C1=C2, Membrane potential, EM should be zero. However, a
small potential is developed on the membrane i.e. EM≠ 0. This is due to the difference in the
radius of curvature of the glass membrane as a result of the difference in strain on the two
surfaces of the membrane, a mechanical abrasion on the outer surface during use, and
chemical etching of the outer surface.
Eg = L + 0.0591 log C1 + Eref + Easym
0
Eg = E g + 0.0591 log C1
0
Eg = E g – 0.0591(-logC1)
Where (-log C1) = -log [H+] = pH
0
Eg = E g – 0.0591 pH
0
Where E g is the combination of three constants, L, Eref and Easym.
Measurement of pH of the given solution using glass electrode.
Cell representation:
Hg| Hg2Cl2| KCl || test solution | Glass| HCl (0.1M) |AgCl | Ag
The cell consists of a glass electrode as an indicator electrode and a
saturated calomel electrode as a reference electrode, the cell is immersed
in a solution whose pH is to be determined. Emf of the cell is measured
using a potentiometer.
Ecell = Ecathode – Eanode
Ecell = Eg – ESCE
0
Ecell = [E g – 0.0591 pH] – ESCE
0
Ecell = E g - 0.0591pH - 0.2422
0
pH = E g – Ecell – 0.2422
0.0591
0
Evaluation of E g
The above cell assembly is placed in a solution of known pH and emf of the cell is
measured using a potentiometer
0
E g = 0.2422 + 0.0591 pH + Ecell
0
Evaluation of E g is essential since it varies with a glass electrode and the reference
electrode.
Types of Electrodes
The classification of electrodes not only depends on electrode material but the full
electrode system comprising of electrode and electrolyte as well as additional substances that

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may be involved in the reaction.

Electrodes can be classified as
i. Metal – metal ion electrode
Metal in contact with a solution containing its own ions.
Ex. Zinc rod in contact with ZnSO4 solution (Zn/Zn2+).
ii. Metal – metal salt ion electrode
Metal in contact with insoluble or sparingly soluble salt as a solid phase next to the
electrode immersed in a solution containing common anion.
Ex. Calomel electrode consisting of mercury in contact with insoluble mercurous
chloride in contact with KCl solution is an example for this type (Hg/Hg2Cl2/KCl).
iii. Gas electrodes
Electrode system in which one of the electrode materials is a gas, bubbled over inert
metal in contact with a solution containing ions or Electrodes at which gases are evolved
or consumed are called gas electrodes.
Ex. Hydrogen electrode (Pt/ H2/HCl).
iv. Amalgam electrode
Amalgam of a metal in contact with solution containing its own metal ions. Highly
reactive metals are used in the form of amalgams since the activity of the metal can be
varied.
Ex. Zinc in mercury in contact with zinc sulphate solution [Zn2+/Zn(Hg)].
v. Redox electrode
Inert electrode in contact with a solution containing metal ions of different oxidation
states.
Ex. Platinum electrode in contact with a solution containing mixture of Fe2+ and Fe3+ ions
[Pt/Fe2+(a1), Fe3+(a2)].
vi. Ion selective electrodes
Electrodes which have the ability to respond to specific ions.
Ex. Glass electrode which responds to hydrogen ions (Ag/AgCl/HCl/Glass).
Concentration cells
Electrolyte concentration cells
Two like electrodes immersed in electrolytes containing its own ions of varying concentrations
constitutes a concentration cell.
Or
It is a limited form of a galvanic cell that has two equivalent half cells of the same material
differing only in concentration.
The driving force for the cell reaction is the difference in the concentration of electrolyte and
the tendency for the solution concentrations to become equalized. Electrical energy is derived
from the free energy change accompanying the transfer of material from a higher concentration
to a lower concentration.

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Concentration cell is represented as

M | Mn+ (C1) || Mn+(C2)| M
Ex.s
1. Two copper rods are separately placed in a solution containing Cu2+ ions of different
concentrations.
Cu |Cu2+ (M1) || Cu2+ (M2)| Cu
2. Two silver rods are separately placed in a solution containing Ag+ ions of different
concentrations.
Ag | AgNO3 (M1) || AgNO3 (M2)| Ag
The above cells are called concentration cells with transference; they include the liquid
junction potential. These are also called electrolyte concentration cells.

The cell reaction is spontaneous when C2>C1. As the cell reaction proceeds, the solution which
was originally more concentrated (C2) becomes dilute and the solution which was originally
dilute (C1) becomes more concentrated. After some time, the concentration of the solution at
both the half cells becomes equal i.e., C1=C2 and the emf of the cell becomes zero. The cell is
in equilibrium. Hence in a concentration cell, emf depends on the ratio of concentrations of the
solutions, as the ratio changes, emf also changes and when the ratio is 1 i.e. C2/C1 =1, emf is
zero.
Emf of a concentration cell
Consider a concentration cell,
M| Mn+ (C1) || Mn+ (C2)| M
Emf of the cell is given by,
Ecell = Ecathode – EAnode

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0.0591 0.0591
E cell = [E 0 Mn+ /M + logC2 ]-[E 0 M n+ /M + logC1 ]
n n
0.0591 0.0591
E cell = logC2 - logC1
n n
In a concentration cell, both anode and cathode are made up of same metal.
0.0591
E cell = (logC2 -logC1 )
n
0.0591 C
E cell = log 2
n C1
Case (i) When C1=C2, Ecell = zero, cell is in equilibrium
Case (ii) When C2>C1, Ecell is positive, cell reaction is spontaneous
Case (iii) when the ratio, C2/C1 changes, Ecell also changes, C2/C1 = constant then, Ecell is
also constant, :. Ecell α C2/C1
Numerical Problems
1. A Concentration cell was constructed by immersing two silver electrodes in 0.05 M
and 1M AgNO3 solution. Write the cell representation, cell reactions and calculate
the emf of the cell.
Ans. Cell representation,
Ag|AgNO3 (0.05M) ||AgNO3 (1M) |Ag
+
At Anode : Ag → Ag (0.05 M) + e-
+ -
At cathode: Ag (1M) + e → Ag
---------------------------------------------------
+ +
Net cell reaction, Ag (1M) → Ag (0.05M)

2. The spontaneous Galvanic Cell Tin | Tin ion (0.024M)|| Tin ion (0.064M|Tin develops
0
an emf of 0.0126 V at 25 C, Calculate the Valency of Tin.

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Ans.
0
3. The emf the cell Cd|CdSO4(0.0093M) ||CdSO4(xM) | Cd is 0.086 V at 25 C. find the
value of X
Ans. n = 2, C2 = x, C1 = 0.0093
Ecell = 0.086 V

4. Represent the cell formed by the coupling of two copper electrodes immersed in
CuSO4 solutions concentration of cupric ions in one electrode system is 100 times
more concentrated than the other. Write the cell reaction and calculate the potential
at 300 K.
Ans. Cu |CuSO4 (X M) || CuSO4 (100X M) |Cu
C2=100x, C1 = X, n=2
At anode, Cu → Cu2+(X M) + 2e-
At cathode, Cu2+(100 M) + 2e- → Cu
Net cell reaction, Cu2+(100 M) → Cu2+(X M)

5. Calculate the cell potential of the following cell at 298K.

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Ag |AgNO3 (0.005 M) || AgNO3 (0.5 M) |Ag

0.0591 C
E= log 2
n C1
n =1
C1 = 0.005
C2 = 0.5
0.0591 0.5
E= log
1 0.005
E = 0.1182V
6. The cell potential of Ag concentration cell is Ag |AgNO3 (0.002 M) || AgNO3 (X M) |Ag
is 0.0751 at 250C. Write the cell reactions and calculate the value of X.
0.0591 C
E= log 2
n C1
n =1
C1 = X
C2 = 0.002
E = 0.0751V
0.0591 X
0.0751 = log
1 0.002
X 0.0751
log = = 1.27
0.002 0.0591
log X = 1.27 + log 0.002
log X = −1.429
X = 0.0372 M

Corrosion Chemistry
Introduction
Corrosion is the process of gradual degeneration of a metal/alloy from its surface due to
chemical or electrochemical interaction with the surroundings resulting into the formation of
compounds such as oxides, sulphides, carbonates, etc.
Example:
The corrosion of iron is called rusting and the corrosion of silver is called tarnishing
Dry or chemical Corrosion
Dry corrosion: It mainly occurs in the absence of aqueous environment, through the direct
chemical action of atmospheric gases such as O2, halogen, H2S, SO2, NOx or anhydrous
inorganic liquid with metal surfaces in immediate proximity.
Most of the corrosion occurs due to electrochemical reactions on the surface of a metal is
known as Wet corrosion.
Electrochemical Theory of corrosion of iron

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Electrochemical theory of corrosion satisfactorily explains the corrosion taking place on the
metal due to electrochemical reactions. According to electrochemical theory, the corrosion of
metals takes place due to formation of galvanic cells generally when a metal is in contact with
Conducting medium containing
i) different concentration of oxygen/air ((A metal area that is exposed to less oxygen
concentration acts as the anode and the metal surface, which is exposed to more
oxygen acts as the cathode).
ii) wo dissimilar metals in contact with each other (Eg. if copper and iron are in
contact with each other, Fe acts as an anode, and Cu behaves as a cathode due to
the difference in electrode potential).
iii) stress on metals due to diverse operations (area under stress acts as anode)
Thus anodic and cathodic regions are formed in presence of conducting medium (like
moisture)
I. At anode: Oxidation of metal in anodic areas or parts generates metal ions and liberates
electrons

M Mn+ (aq) + ne- (at anode)

(a) Hydrogen evolution (b) Oxygen absorption

For Eg When a chemically non-uniform surface of iron is in contact with conducting medium,
a galvanic cell is formed, iron becomes the anode, and impurity develops as the cathode.
At anode, Fe undergoes oxidation
Fe → Fe+2 + 2e-
The electrons are transferred through the metal from anode to cathode constituting corrosion
current.
II At the cathode region: Reduction reaction occurs at the cathode and it relies on the nature
of the environment/electrolyte. Cathodic reactions are of two types, hydrogen evolution and
oxygen absorption type.
The formation of the corrosion product depends on the availability of the oxygen in the
medium.
a) In acidic medium:
i) Liberation of hydrogen takes place in the absence of oxygen
2H+ + 2e- → H2 ↑

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ii) In the presence of oxygen, absorption of oxygen takes place

4H+ + O2+ 4e- → 2H2O
b) In basic or neutral medium:
(i) In the absence of dissolved oxygen, metal hydroxides are formed in addition to the
liberation of hydrogen, as
2H2O+ 2e- → 2OH- + H2 ↑
(ii) In the presence of dissolved oxygen the metal hydroxides/oxides are formed.
O2 +2H2O + 4e- → 4OH-

III Corrosion product

The diffusion of metallic (Fe2+) and non-metallic ions (H+, OH-) takes place towards each other
through the conducting medium and corrosion product is formed near the cathodic site. (The
site of corrosion product formation depends on the mobility of metal ions and non-metallic
ions).
Net reaction:
Fe+2 +2 OH- →Fe(OH)2↓(Ferrous hydroxide)
(i) The ferrous hydroxide is unstable in oxygenated solutions, further it is oxidized to ferric
salt.
2 Fe(OH)2+ H2O + ½ O2 → Fe(OH)3↓ (rust)
4 Fe(OH)2+ 2H2O + O2 → 2[Fe2O3. 3H2O]
(yellow rust, Haematite)
(ii) If the supply of oxygen is limited, hydrated ferrosoferric [Fe(II),Fe(III)] oxide is formed.
3 Fe(OH)2 + ½ O2 → Fe3O4.3H2O or Fe2O3.FeO.3H2O
(black rust,magnetite)
During the corrosion of metal, the rate of oxidation and reduction are equal (in terms of
production and consumption of electron) and the total current due to the cathodic reaction (Σic)
is equal, but opposite in sign to the total current flowing out of the anodic reaction (-Σia). icorr
= - Σia= Σic
Further, the rate of corrosion depends on the nature of the product. If the product is
soluble/volatile/ unstable, the metal suffers from severe corrosion, if the product is insoluble
and stable, prevents the metal from further corrosion.
Types of Electrochemical Corrosion:
1. Differential metal corrosion or Galvanic corrosion

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Galvanic corrosion, also known as bimetallic corrosion, is an electrochemical process whereby

one metal corrodes in preference to another metal that it is in contact with through an
electrolyte. The metal higher up in the electrochemical series (with more negative electrode
potential) will form anode and experience corrosion while the other metal lower in the
electrochemical series acts as the cathode and is free from corrosion.

In a bimetallic couple, the less noble metal will become the anode of the corrosion cell and
tend to corrode at an accelerated rate, compared with the uncoupled condition. The more noble
metal will act as the cathode. Galvanic corrosion can be one of the most common forms of
corrosion as well as one of the most destructive.
For example, if aluminium and carbon steel are connected and immersed in seawater,
aluminium being anodic to steel, will corrode more quickly, whilst steel will receive protection.

Eg: a) Zn & Ag couple (Zn is anodic to Ag and experiences corrosion, Ag remains

cathodically protected),
b) Fe & Cu couple (Fe being anodic to Cu undergoes corrosion, Cu remains cathodically
protected),
c) Zn & Fe couple (Zn being anodic to Fe undergoes corrosion, Fe remains cathodically
protected),
d) Mg & Zn couple (Mg is being anodic to Zn suffers corrosion, Zn remains cathodically
protected),
e) Brass containing copper and zinc. Since zinc is anodic to copper, selective dezincification
occurs in a corrosive medium, enriching the cathodic copper in the matrix and the colour
of brass turns red from yellow.
f) Graphitization of gray cast iron: graphite being cathodic enhances dissolution of iron
in the matrix, leaving behind a graphite network.

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g) Precious metal alloys such as gold containing copper or silver: In strong acids, (or
sulfide environment) preferential dissolution of copper or silver takes place.
Mechanism: Steel (Fe) has lower electrode potential than copper, acts as anode and electrons
flow from the anodic metal (Fe) to cathodic metal (Cu). The anodic metal is corroded while
the cathodic metal remains protected.
Eg: Fe/H+(aq)/Cu is similar to a chemical cell.
Iron undergoes oxidation liberating electrons, Fe → Fe2+ (aq) + 2e-
In acidic solution, the corrosion occurs by the evolution of hydrogen at the cathode
2H+ (aq) + 2e- → + H2
In neutral or alkaline medium, oxygen absorption takes place.
H2O+½ O2 + 2e- → 2OH-
The formation of rust as Fe2O3.xH2O (yellow) or Fe3O4.xH2O (black) depends on the
availability of oxygen in the medium.
If oxygen is sufficient in the medium, the following reactions take place.
2Fe2+ + 4OH- → 2 Fe (OH)2
2Fe(OH)2 + O2 +(n-2)H2O → Fe2O3 . nH2O (rust)
Other common examples are
i) Steel pipe with brass fittings
ii) Lead –antimony solder around the copper wire
iii) Water heaters with copper tubes & cast iron or steel tube sheets.
iv) Galvanic corrosion of aluminum shielding in buried telephone cables.
v) Galvanic corrosion of the body of the ship in contact with brass or bronze propellers.
vi) Galvanic corrosion on a gannet wheel where the steel securing the bolts is in contact with
the magnesium wheel.
vii) Galvanic corrosion between the tubes and the tube sheet in heat exchangers.
viii) Aluminum conduit buried in steel reinforced concrete.
ix) Galvanic corrosion of steel coated with copper due to the defects in copper coating.
x) Galvanic corrosion of the Statue of Liberty.
xi) Galvanic corrosion inside horizontal stabilizers in aircrafts.
Note:
The rate of corrosion depends on
i) the amount of current passing through anode & cathode
ii) difference in electrode potentials between anode and cathode (larger the difference,
more the current flow and faster is the rate of corrosion)
iii) the ratio of the anodic area to cathodic area, environmental factors and the tendency of
the metal to exhibit passivity etc.
iv) conductivity of electrolyte

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Galvanic Series:
Electrochemical series can not be taken as a reference to explain galvanic corrosion taking
place in all bimetallic couples as there are few exceptions. For example, Electrochemical series
fails to explain corrosion taking place on zinc when it is in contact with aluminium and
corrosion of silver when it is in contact with titanium. Hence a more practical series called the
galvanic series has been developed to explain corrosion taking place in bimetallic couples. The
galvanic series is a more accurate representation of actual galvanic corrosion characteristics
than the emf series.
The series in which the metals and alloys are arranged in decreasing order of their oxidation
potential by measuring the same using standard calomel electrode as the reference electrode
and immersing the metals and alloys in sea water is called galvanic series.
A list of metals and alloys arranged according to their relative electrolytic potentials to one
another in a given environment. The metals or alloys, higher on the list (more negative) are
anodic to those lower on the list (cathodic). The galvanic series determines the nobility of
metals and semi-metals. When two metals are submerged in an electrolyte, while electrically
connected, the less noble will experience galvanic corrosion. The galvanic series listing the
common metals and alloys given below, from which the relative corrosion tendencies can be
judged.

More anodic: Mg, Mg alloys, Zn, Al, Cd, Fe, Pb, Sn, Ni–Mo–Fe alloys) Brasses, Cu, Ni, Cr–
steel alloy, Ag, Ti, Au, Pt towards noble nature.
The metal/alloy, higher up in the series corrodes faster than the metals/alloys in the bottom of
the series. The greater the difference in their positions in the galvanic series faster will be the
rate of corrosion. Metals close to each other in the galvanic series demonstrate a lesser tendency
to corrode when in contact with each other. Metals like Ti (placed below Ag in the galvanic
series, but above in emf series) and Al (placed below Zn in the galvanic series, but higher in
emf series) exhibit exceptional resistance to corrosion because of Passivation.
Note: Passivation: It is the phenomenon of protection of metals against atmospheric corrosion
due to the formation of a thin layer of continuous, non-porous and adherent film of metal oxide.
The film (like TiO2 on Ti and Al2O3 on Al) forms a barrier between the corroding environment
and metal.

Comparison between Galvanic Series Vs Electrochemical Series:

Galvanic Series Electrochemical Series

It predicts the corrosive tendencies of metal It predicts the relative displacement

& alloys. tendencies of metals with respect to H2.
Calomel electrode is used as a reference The standard hydrogen electrode is used as
electrode. a reference electrode.
The metals and alloys are immersed in the The metals are immersed in 1 M
seawater for study. concentration of salt solution containing its
own ions.

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Position of metal or alloy may change. Position of metal is fixed.

Electrode potentials are measured only for Electrode potentials are measured for both
metals and alloys. metals.

2. Differential aeration corrosion (Concentration cell corrosion)

Corrosion of metals occurs when the metal surface is exposed to an electrolyte of varying
concentrations or different air concentrations. In differential aeration corrosion, the area with
the higher oxygen concentration becomes the cathode, and the area with the lower oxygen
concentration turns into the anode. Thus, the portion of the metal that has the lower oxygen
concentration is the portion that corrodes.

Example: Zn/O2 (lower concentration) // O2(higher concentration)/Zn

Consider a strip of Zn rod partially immersed in an aerated solution of seawater. The

concentration of oxygen is high at the surface (adjacent to the waterline) than inside the solution
acts as a cathode, while the part of the metal immersed in the solution has a reduced amount of
oxygen and acts as an anode. Therefore, a difference of potential causes the flow of electrons
among the two unequally aerated areas of the same metal. Oxidation takes place at anode, Zn
→ Zn2++2e-
The electrons flow from anode to cathode, and reduction takes place at the cathode.
H2O + O2 + 2e- → 2OH-

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Some of the common examples of differential aeration corrosion are

1. Metals under dirt, dust, scale, wood, plastics, rubber, glass, concrete, asbestos, wax, and
fabrics undergo corrosion.
2. Partially buried pipeline in soil or submerged in water undergoes corrosion below the soil
or water, whereas the exposed part suffers no corrosion.
3. Attack of enameled or lacquered surfaces of food and beverage cans that have been exposed
to the atmosphere show the reddish-brown corrosion filaments.
4. Corrosion occurs at the paper-aluminum interface in Paper-backed aluminum foil.
5. Stainless steel in seawater or ferric chloride solution.
6. Window rods inside the frame suffer corrosion, but not the exposed regions.
7. Part of the nail inside the wall, being exposed to lower oxygen concentration than the
exposed part undergoes corrosion.
Types of differential aeration corrosion
A.Waterline corrosion
Waterline corrosion occurs just below the waterline when there is a variable supply of oxygen
to regions of the same metal component. It is a type of electrochemical corrosion that impacts
metals such as steel and iron. When a poorly oxygenated area is adjacent to an area with a
good supply of oxygen, an anodic and cathodic reaction occurs. Eg., when water is stored in a
metallic tank, the metal below the waterline gets corroded as it is poorly oxygenated (anode)
and the metal above the waterline is highly oxygenated (cathode).
It is particularly common in ships, iron tanks used for storing water, etc., in which a portion of
metal is below, and the other is above the water level. Because of the poor conductivity of
water, the ions just below the water level are more readily available for reaction; therefore, the
metals corrode just below water level that is beneath the waterline).
Mechanism:
The electrochemical reactions are
At Anode : Fe → Fe2+ + 2e- (Oxidation)
At Cathode : 2H+ + O2 +2e- → 2OH-(reduction)

Fe + 2H+ + O2 → Fe(OH)2 Fe (OH)3

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Further, the formation of the products depends mainly on the nature of the medium. Eg., Ships
sunk deep underwater for many years are free from corrosion, whereas ocean-going ships have
practical water line corrosion

B. Pitting corrosion: This is a type of differential aeration corrosion.

Pitting corrosion is a localized form of corrosion by which cavities or "holes" are produced in
the material. Pitting is said to be more destructive than uniform corrosion damage because it
is more difficult to detect, predict and design against. Corrosion products often cover the pits.
Pitting corrosion, which, for example, is almost a common denominator of all types of localized
corrosion attack, may assume different shapes.

The driving power for pitting corrosion is the

depassivation of a small area, which becomes anodic, while an unknown but potentially vast
area becomes cathodic, leading to very localized corrosion.
Pitting is considered to be more dangerous than uniform corrosion damage since i) it is more
difficult to detect, predict and design against. ii) A small, narrow pit with the tiniest overall
metal loss can lead to the failure of an entire engineering system. ii) Pits usually grow in the
direction of gravity. iv) Most pits develop and grow downward from horizontal surfaces. Lesser
numbers start on vertical surfaces and very rarely do pits grow upward from the bottom of
horizontal surfaces v) The corrosion penetrates the mass of the metal, with limited diffusion of
ions. Pits are sometimes isolated or so close together that they look like a rough surface.
Pitting corrosion is due to
i) Metal surface is not homogeneous, ii) External environment is not homogeneous, iii) Films
are not perfectly uniform, iv) Crystallographic directions are not equal in the reactivity and v)
Environments are not uniform concerning concentration.
Factors influencing pitting: Cl- content, pH value, temperature, presence of oxidizing agents.
Mechanism: A small part of the metal surface covered by an impurity like dust, rust, sand,
scale, or water has a low oxygen concentration and it acts as anode and gets corroded. The rate
of this type of corrosion accelerates with time since the product of corrosion deposits very close
to the anode, creating more anodic zones. They become the foci for the corrosion, inducing
localized spots, pinholes, cavities in the metal. Whereas the uncovered metal surface acts as a
cathode due to the high concentration of oxygen. Once the small pit is formed, the rate of
corrosion increases.

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The consequent
electrochemical reactions are
At anode: Fe →Fe2+ +2e-
At cathode: ½ O2+H2O + 2 e- →2OH-
Fe + H2O + ½ O2 →Fe(OH)2 →Fe (OH)3

Corrosion protection
Cathodic protection by sacrificial anodic method
Sacrificial protection is a corrosion protection method in which a more electrochemically
active metal is electrically attached to a less active metal. The highly active metal donates
electrons to substitute those which may have been lost during oxidation of the protected metal.
The process reverts the protected metal to its original form and thereby prevents it from
corroding.
In this method, the current required for cathodic protection is supplied by the corrosion of an
active metal. Sacrificial anode systems rely upon the differences in corrosion potential that are
established by the corrosion reactions that occur on different metals or alloys. The more active
metal will become anodic by providing electrons for the cathodic protection of a less active
metal (nobler). The more active metal (anode) is sacrificed to protect the less active metal
(cathode).
Process: The less noble metals like Zn, Mg, Al or their alloys other than the metal to be
protected is used as the anode and is consumed during the protection of steel structure (or any
structure). The metal structure to be protected will act as a cathode. The electrons for the
protection, in this case, are supplied by the dissolution of the sacrificial anode.
Eg., Typical sacrificial protection is where a more reactive metal is used as a sacrificial anode
by attaching it to ship hill, steel pipes or pump bodies. Iron becomes a cathode that does not
corrode while the anode corrodes to provide the desired sacrificial protection..

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Fig: Protection of an underground pipeline with a magnesium anode

Advantages:
Low cost, provides protection without power requirement, Does not require maintenance,
Simple installation and operation.
Disadvantages:
Periodic replacements of the anode, Increased noise level from the anodes, Current output
cannot be regulated, Periodic replacement costs, especially in ships since they must be dry
docked.
Galvanizing: The Coating of Zinc on iron/steel by hot dipping is known as galvanizing. It is
the most common procedure used to protect the iron and its alloys from corrosion. In
Galvanizing, zinc combines with iron to form an alloy, which varies in composition from the
outer layer to the iron.
Process:
1. Iron or steel article is first cleaned with alkali followed by a dilute solution of sulphuric acid
(pickling). The pickling process removes any scale, rust, oxide layer, and impurities. The article
is then subjected to preliminary treatment which consists in treating with 5% Hydrofluoric acid
to dissolve grains of sand, on the surface of the article. To clean any superficial oxide, the
article is subjected to cleaning by passes through 5-20% zinc ammonium chloride solution.
2. The article is finally washed with distilled water and dried and dipped in a bath of molten
zinc covered with ammonium chloride flux at about 425-450 ℃.
3. This process is called a zinc bath treatment in which the surface of the bath is covered with
a flux to avoid oxide formation.
4. The article coated with the zinc layer is then taken out of the bath and passed through a pair
of hot rollers to remove excess/superfluous zinc, and uniform layered thickness is produced on
the article.
5. Finally, the article is annealed at 650 ℃ and then cooled slowly.

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Diagram: Galvanization of Iron

Application: It is commonly used for
i) Protecting iron exposed to the atmosphere
ii) Protecting roofing sheets, wires, pipes, sheet ware, nails, bolts, wire cloth, buckets, tubes,
etc., from atmospheric corroding.
Anodizing or anodized oxide coatings
Anodizing involves the electrolytic oxidation of a surface to produce a tightly adherent oxide
scale that is thicker than the naturally occurring film. Anodizing is an electrochemical strategy
during which aluminium is the anode. The electric current passing through an electrolyte
converts the metal surface to durable aluminium oxide. The difference between plating and
anodizing is that the oxide coating is necessary with the metal substrate as opposed to being a
metallic coating deposition. The oxidized surface is hard and abrasion-resistant, and it provides
some degree of corrosion resistance.
Anodizing on Aluminium
Process: Anodizing of aluminium is carried out by making aluminium as anode in an
electrolytic bath containing a suitable acid-like chromic acid at 35 - 40 ℃. A plate of lead or
stainless steel is made the cathode. When a current of moderate density is passed, the O2
liberated at the anode combines with it to form an oxide which takes the form of a thick film.
At anode: 2Al →2Al3+ (aq) +6e-
2Al + 3H2O → Al2O3 + 6H+
At cathode: 6H+ +6e- → 3H2
Overall reaction: 2Al + 3H2O → Al2O3+3H2↑
Al2O3 deposits on the surface of the object. The thickness of the deposit is controlled by
adjusting the current and the bath solution. The coating is slightly porous, and it is sealed by
dipping in hot water, Al2O3 gets hydrated to Al2O3.H2O, which occupies more volume and
protects the metal from corrosion.
Applications of anodized aluminium:
Anodized aluminium is used for office partition, hardware, lobbies, escalators, elevators and
window frames.

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Corrosion rate
The corrosion rate is the speed at which any metal in a specific environment disintegrates. It
also can be described as the amount of corrosion loss per year in thickness. In the United States,
the corrosion rate is typically computed using Mils per year. The speed or rate of deterioration
depends on the environmental conditions and the type and condition of the metal under
consideration.
Corrosion Penetration Rate (CPR) : 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. It gives the amount of corrosion loss per year in thickness and the speed at which
corrosion spreads to the inner portions of a material. It is expressed interms of Mils penetration
per year(mpy) or millimeter per year(mmpy).
Weight loss method: It is the most commonly used for the measurement of uniform corrosion.
It involves the exposure of a weighed piece of test metal or alloy to a specific environment for
a precise time. This is accompanied by thorough cleaning to remove the corrosion products and
then determining the weight of the lost metal as a result of corrosion.
The corrosion rate is best described in terms of the thickness or weight loss where the surface
of the metal disintegrates uniformly across the area that has been exposed.

The corrosion penetration rate(CPR) is calculated by using the following mathematical

relation:

KW
CPR =
dAt

Where K = constant, K=534, if CPR is in mils per year (1 mil = 0.001 inch) or K= 87.6 if CPR
is in millimeter per year (1 inch= 2.54 cm or 25.4 mm),
W = total weight lost after exposure time ‘t’ in mg
t = time taken for the loss of specimen
A = the surface area of the exposed specimen cm2 for mm/year
d = the specimen density in g/cm³
CPR Units K value Units
W d A t

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mpy 534 mg gcm-3 in2 h

mm/yr 87.6 mg gcm-3 cm2 (1inch2 = 2.542 cm2 = h
6.45 cm2)

Numericals on Corrosion Penetration Rate (CPR)

1. A steel plate having the area of 100 in2 is exposed to moist air in an sugar industry. After a
period of one year, it was found that the material has lost 485 g due to corrosion. Given  steel=
7.9 gcm-3. Calculate the (a) CPR in mpy (b) CPR mm per year (c) Can we apply such steel
plate for the construction purpose where the steel sheet should be exposed.
Solution:
KW
a) CPR =
dAt

K= 534, W= 485x103 mg, d = 7.9 gcm-3, A= 100 in2, t = in hr (365 daysx24hr)

534x485x103
CPR =
7.9 x 100x 365x24
CPR = 37.42 mpy

b) All units are same but only the area shall be converted into cm2, A= 100 in2x2.54 cm2
K= 87.6
KW
CPR =
dAt
87.6x485x103
CPR =
7.9 x 100 x ( 2.54 ) x 365x24
2

= 0.951 mmpy
2. A thick steel sheet of area 400 cm2 is exposed to air near the ocean. After a one-year period
it was found to experience a weight loss of 375 g due to corrosion. To what rate of
corrosion, in both mpy and mmpy, does this correspond?
KW
Solution: CPR =
dAt
a) In mpy
K = 534, A = 400 inch2, t= 1x365x24 hrs
KW
CPR =
dAt
534 x (375 x103 )
CPR = = 46.7 mpy
7.9 x 400 ( 2.54 ) x 24 x 365
2

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b) In mmpy
K = 87.6, A = 400x2.542 cm2, t = 1x365x24 hrs.
87.6x ( 375 x103 )
CPR =
7.9 x 400x24 x365
= 1.19 mmpy
More Problems to work

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
mpy and mmpy. Density of carbon steel is 7.8 g/cm3.
2. Calculate the CPR in mpy and mmpy for a thick steel sheet of area 200 inch2 Which
experiences a weight loss of 500 g after 1.5 years. Density of steel is 7.9 g/cm3.
3. A metal iron was found in a vessel containing acidic media, it was estimated that the
original area was 20 inch2 and 1.2 kg of the metal has corroded. Assuming a CPR of
400 mpy, calculate time in years, density of iron is 7.87 g/cm3.
4. A piece of aluminium was submerged in ocean for 8.5 years. The original area was 64
cm2 And 350 g of the metal was corroded over a period of 8.5 years and the density of
aluminium is 2.7 g/cm3. Calculate CPR in mpy and mmpy.
Analytical Techniques
Types of Instrumental Methods/ physical methods/Modern methods of analysis that relied on
physical properties of analyte, thus generally are not destructive. These methods are not
necessarily more sensitive. They are
1. Electric current or Voltage measurement is called electroanalysis. Example: Potentiometry,
conductometry, pH metry etc.
2. Electromagnetic radiation measurement is called Spectroscopic/radioanalysis. Example:
Emission, absorption, fluorescence, phosphorescence, luminescence, UV-Vis, IR, NMR,
Raman, Nephelometry, X-Ray Diffraction, Polarimetry, circular dichroism etc.
Advantages of Instrumental methods:
1. Rapid analysis, process can be automated and sample throughput is high
2. The methods are highly sensitive, even a small trace or ultra trace quantity of the sample
analysis is feasible.
3. They are highly selective, accurate measurement of a constituent is possible in the presence
of several other components.
4. The results are reliable, objective and reproducible.
5. A small quantity ( mg, mL or even less than) of the sample is sufficient for the analysis
Limitations:
1 Most of the instrumental methods are not economical (Cost of the equipment is high)
2. Sometimes the analysis is complex in nature and many signal many leads to confusion.
3. Maintenance is required and operation of the equipment required the learned technician.
4. Instrument necessitates calibration with reference to the standard material as reference
substance.

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Conductometry:
Introduction: Conductometry involves the determination of the electrical conductivity of a
solution to monitor the progress of a chemical reaction. It determines the quantity of a material
present in a mixture by measuring its effect on the electrical conductivity.
Factors affecting conductance:
1. Temperature: The conductance of an electrolyte solution increases proportionately with the
increase in the temperature owing to a rise in the extent of ionization.
2. Nature of electrolyte: The strong electrolytes experience complete ionization and
consequently exhibits higher conductivities because they furnish the number of ions. While
weak electrolytes undergo partial ionization and therefore display comparatively low
conductivities in their solutions.
3. Ionic size, mass & mobility: The velocity with which ions move under the influence of an
electric field is inversely proportional to the mass and the size of the ions. The ion mobility
(movement of charged particles under the influence of an applied electric field) decreases
with an increase in the size and mass hence, the conductivity decreases. E.g. In the molten
state, the conductivities of lithium salts are higher than those of Caesium salts due to the
smaller size of the Li+ ion than that of Cs+ ion.
4. Concentration: The specific conductance (κ) rises with an increase in the strength of a
solution as the number of ions per unit volume increases. Whereas, both the equivalent
conductivity and molar conductance raise with a decrease in concentration (i.e. Upon
dilution) as the extent of ionization increases.
Types of conductances:
1. Equivalent conductance:The conductance of one gram equivalent of solute contained
between electrodes spaced unit distance apart is called equivalent conductance.
2. Molar conductance: "The conductance caused by all the ions in a unit volume of solution
containing unit mole of the electrolyte having placed the electrodes unit distance apart.
3. Specific conductance(κ): Specific conductance the measure of conductance by placing a cell
having a unit area(A) of a cross section of the electrode and are placed at the unit distance (L)
apart.
Principle: The principle of measurement of conductivity includes the use of a conductivity cell
(consisting of two platinum electrodes placed) in the analyte (sample) solution, and a potential
is applied across them. The conduction of electricity in a sample solution is because of the
migration of cations and anions towards the respective cathode and anode. Though the
movement of the ions occurs in the solution, it remains electrically neutral throughout. The
mobility of an ion takes place under the influence of an applied voltage or a concentration
gradient. It is affected by various factors such as the charge, size, mass, and extent of salvation.
ConductivityC), the inverse of the resistivity(R), is determined from the voltage and current
values(I) according to Ohm’s law.
C= I/R
It is expressed in terms of Siemens(S) or mho. Specific conductivity(κ) simply is the measure
of conductance by placing a cell having a unit area of a cross section of the electrode and placed
at a unit distance apart. This expressed as
κ=C×L/A μScm-1 or mScm-1

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Instrumentation:
1. Conductivity cell – it is constructed by a Pyrex or other resistance glass fitted with a pair of
Pt or platinized electrodes.
2. Conductivity meter- to display the reading during titration.
3. Thermostat- to maintain the constant temperature.
4. Magnetic stirrer- the conductivity cell is dipped in the analyte solution and placed on the
magnetic stirrer to maintain the uniform concentration after each addition.

Experimental: A simple arrangement for the measurement of conductance is shown in Fig.

The analyte solution whose conductance is to be estimated is taken in a beaker. The
conductivity cell is dipped in the solution and mixed with using magnetic stirrer and, a constant
temperature is maintained with the help of a thermostat. Further, it is connected to the
conductivity meter and initial conductance is measured. The titrating reagent is added in small
proportions, and conductance of the solution is measured after stirring. The addition of the
titrating reagent is continued until at least five readings beyond the equivalence point. A graph
is prepared by plotting the conductance readings against the volume of the titrating reagent.
The two straight portions of the curve are extrapolated until they intersect and the point of
intersection is taken as the equivalence point of the titration.
Weak acid with a strong base:
[CH3COO - + H+ ] + [Na+ + OH- ] [CH3COO - + Na+ ] + H2O
In the titration of a weak acid (Ka ≈ 10-5) with a
strong base, the shape of the curve depends
upon the concentration and dissociation
constant Ka. In the titration of the acetic acid
with sodium hydroxide solution, the salt,
sodium acetate, which is formed during the first
part of the titration tends to oppose the
ionization of acetic acid still present and hence
the conductance decreases. The rising salt
concentration will, however, tend to increase
the conductance of the solution as shown in the
figure. Owing to these opposing influences the
titration curves may have minima and its position depend upon the concentration as well as the
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strength of the weak acid.

4. Weak acid with a weak base:

[CH3COO - + H+] + [NH4+ + OH-] [CH3COO - + NH4+ ] + H2O

The titration curve of a weak acid with a weak base is displayed. The neutralization curve up
to the equivalence point is similar to that obtained with sodium hydroxide solution because
both sodium and ammonium acetates are strong electrolytes. After the equivalence point, the
addition of ammonia solution has little effect upon the conductance due to supressing the
ionization of ammonia by ammonium acetate salt present in the solution.
ADVANTAGES OF CONDUCTOMETRIC TITRATIONS
a) No need of indicator.
b) Colored or dilute solutions or turbid suspensions can be used in titrations.
c) Temperature is maintained constant throughout the titration.
d) The endpoint can be determined accurately and errors are minimized as the end point is
being determined graphically.
Potentiometry
Introduction: Potentiometry is used as a technique in chemical analysis. It is the measurement
of electrical potential at an electrode relative to some reference in the absence of current flow.
It is usually employed to find the concentration of a solute in a solution.
Principle: The direct potentiometry provides a rapid and convenient method for the
measurement of electrode potential that determines the concentration or activity of a variety
ionic species in solution.
The change in potential at the electrodes is proportional to the variation in the concentration of
the analyte solution. It is a comparative method that compares the potential developed across a
cell containing the indicator electrode and a reference electrode and its value is given by the
Nernst equation.
0.0591
𝐸 = 𝐸0 + log⁡[𝑀𝑛+ ]
𝑛
or
0.0591 [𝑜𝑥𝑑]
𝐸 = 𝐸0 + log
𝑛 [𝑅𝑒𝑑]

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The potential of the indicator electrode changes with the variation in concentration of the
analyte ion, the change in EMF is measured against the change in volume of the titrant added
using an electrochemical cell consisting of reference electrode, indicator electrode and a salt
bridge. And the results interpreted by graphical methods. The equivalence point will be
revealed by a sudden change in the plot of e.m.f readings against the volume of the titrating
solution.
Instrumentation:
The essential parts of the potentiometer are
i) An indicator electrode: An indicator electrode is a working electrode whose potential
depends on the concentration of the ion/activity of analyte solution.
ii) A reference electrode: reference is an electrode which has the fixed potential and it is
completely insensitive to the nature or composition of the analyte solution.
Eg: Calomel electrode, Silver-silver chloride electrodes
iii) A salt bridge if necessary
iv) A meter to determine the difference in potential

Experimental :
A simple arrangement for Potentiometric titration is exhibited in Fig. It consists of a reference
electrode (Saturated calomel electrode), indicator electrode (like Platinum electrode) and a
magnetic stirrer. The analyte solution is contained in the beaker. The EMF of the cell containing
the initial solution is determined. The standard solution is added in equal increments and the
e.m.f is measured after each addition. The approach of the equivalence point is indicated by a
relatively rapid change of the e.m.f. Several readings should be taken even after the endpoint.
Location of end points: The endpoint of a Potentiometric titration can be easily located by
examining a Gran’s Plot. Three procedures can be adapted to fix the exact endpoint. They are
(a) the method of bisection (b) the method of parallel tangents and (c) the method of circle
fitting.

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Dr. Roopashree B, JSSATEB
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When titration curves are obtained by plotting a graph of e.m.f against the volume of titrant
added, an S-shaped curve is obtained. From the central portion of the steeply rising portion of
the S-shaped curve, the endpoint can be clearly located.
A more sensitive and satisfactory method of finding the endpoint is to plot the first derivative
curve against volume. (i.e., ΔE/ΔV versus V), it gives a maximum inflation at the end point or
the second derivative curve against volume (i.e., Δ2E/Δ2V versus V) of the titrant, the endpoint
is determined at the zero value.

Example:
The titration of FAS solution with K2Cr2O7 in the presence of H2SO4 using Pt electrode as an
indicator electrode and the calomel electrode as a reference electrode.
The presence of an oxidized and reduced form of the same substance in a solution gives
rise to the formation of the oxidation-reduction electrode, developing an electrode potential,
which can be picked up by dipping a platinum wire.
3Fe2+ + Cr6+ → 3Fe3+ +Cr3+
Thus, when the titration is commenced, both Fe3+ and Fe2+ ions are present in the solution,
developing an electrode potential, which is picked up by a platinum electrode. Thus (Pt/Fe3+,
Fe2+) is the indicator electrode, whose electrode potential is given by,
0.0591 [𝐹𝑒 3+ ]
𝐸 = 𝐸0 + log⁡
𝑛 [𝐹𝑒 2+ ]
It is combined with a reference electrode (calomel electrode) and the emf of the cell is
measured. The equivalence point is determined by plotting the graph of ΔE/ΔV against the
volume of K2Cr2O7 as indicated Fig.
Applications:
Potentiometric titrations are used
1. To determine the pH of a given solution employing glass/calomel electrode.

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Dr. Roopashree B, JSSATEB
 MODULE-3 22CHES12

2. Complexometric titrations can be followed with an electrode of the metal whose ion is
involved in complexometric titrations.
3. It is used in redox titrations using an inert electrode.
4. They are used in precipitation titrations that involves insoluble salts of metals like silver,
mercury, lead, and copper.
5. Potentiometric titrations are also used for carrying out titrations in non-aqueous solvents.
The ordinary glass-calomel electrode can be used.
Advantages of Potentiometric Titrations
Potentiometric Titrations have many advantages over indicator methods
1. The apparatus required in general inexpensive, reliable and readily available.
2. It is easy to interpret titration curves.
3. It can be used for colored solutions, applicable for analysis of dilute solutions.
4. Several compounds can be titrated in the same solution without the possibility of indicators
interfering with each other. Eg. Bromide and iodide may be titrated together.

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Dr. Roopashree B, JSSATEB