BGS COLLEGE OF ENGINEERING

& TECHNOLOGY
DEPARTMENT OF APPLIED CHEMISTRY
MAHALAKSHMI, Bengaluru - 560086

APPLIED CHEMISTRY (BCHES102/202)

Corrosion control & Electrode system BGSCET-2023

CORROSION AND ELECTRODE SYSTEM

Syllabus:
Corrosion chemistry: Introduction, electrochemical theory of corrosion, types of corrosion-
differential metal and differential aeration. Corrosion control - galvanization, anodization and
sacrificial anode method. Corrosion Penetration Rate (CPR) – Introduction and numerical
problem.
Electrode System: Introduction, types of electrodes. Ion selective electrode – definition,
construction, working and applications of glass electrode. Determination of pH using glass
electrode. Reference electrode - Introduction, calomel electrode – construction, working and
applications of calomel electrode. Concentration cell– Definition, construction and Numerical
problems.
Analytical Techniques: Introduction, principle and instrumentation of Conductometry; its
application in the estimation of weak acid. Potentiometry; its application in the estimation of
iron.

CORROSION
Corrosion:
It is defined as the destruction and consequent loss of metals due to chemical or
electrochemical attack on its surface by the surrounding environment.
Electrochemical theory of corrosion:
According to electrochemical theory, corrosion of metals occurs due to the following
changes, when they are exposed to the environment.
1. A large number of minute galvanic cells are formed which acts as anodic and cathodic
areas
2. At anode the metal undergoes oxidation and electrons are liberated which migrates towards
cathodic region.
3. Oxygen of the atmosphere undergoes reduction at cathodic area in the presence of moisture
forming hydroxide ions.

Corrosion Reaction:
1. Anodic Reaction: At anode the metal undergoes oxidation and liberating electrons.

Fe Fe2++ 2e-

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Corrosion control & Electrode system BGSCET-2023

2. Cathodic Reactions: At cathode, reduction occurs due to the consumption of electrons

generated at the anode. The different cathodic reactions are:
 In acidic medium: If the metal surface is exposed to acidic medium, in the absence of

air, then hydrogen ions are reduced to hydrogen gas.

2H+ + 2e- H2
 In alkaline and deaerated medium: If the metal surface is exposed to only
moisture under alkaline medium, in the absence of air, then water is reduced to OH-
ions and H2.
2H2O + 2e- 2OH- + H2 ↑
 In neutral and aerated medium: If the metal surface is exposed to moisture and air,
under neutral medium, then oxygen is reduced to OH- ions.
H2O + ½ O2 + 2e- 2OH–
3. Formation of rust:
 The Fe2+ ions formed at anode move towards cathode and OH- ions formed at
cathode move towards anode. As Fe2+ ions diffuse faster than OH- ions, they meet
near the cathode forming ferrous hydroxide.
Fe2+ + 2OH- Fe (OH)2
 Ferrous hydroxide further reacts with O2 and H2O forming reddish brown
hydrated ferric oxide (rust).
4Fe (OH)2 + O2 + 2H2O 2[Fe2O3.3H2O]
(Rust)
Factors influencing the rate of corrosion:
a) Nature of the corrosion product:

If the corrosion product is insoluble, stable, uniform and nonporous, it acts as a barrier
(protective film) between the fresh metal surface and surrounding corrosion environment
and preventing the further corrosion.
Example: Al, Cr & Ti
If the corrosion product is soluble, unstable, non-uniform and porous, do not form
protective film. In such cases, the fresh metal surface is continuously exposed to the
surrounding corrosion environment and corrosion of the metal takes place continuously.
Example: Zn, Fe & Mg.

b) The ratio of anodic to cathodic area:

If the anodic area is smaller and cathodic area is larger (i.e., the ratio of anodic to cathodic
area is small), the electrons liberated at the anode, are rapidly consumed at the cathodic
area. This makes the anodic reaction to take place at a faster rate, thus increasing the rate
of oxidation and corrosion.
Example: Coating of tin on iron.

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Corrosion control & Electrode system BGSCET-2023

If the anodic area is larger and cathodic area is smaller (i.e., the ratio of anodic to cathodic
area is large), the consumption of electrons liberated at the anode will be slower at cathode
area and therefore rate of oxidation at anode decreases and corrosion rate also decreases.
Example: Coating of zinc on iron.

Nature of surrounding medium

c) pH:

Acidic medium is generally more corrosive than alkaline and neutral medium. Lower the
pH of the medium (below 3), severe corrosion occurs even in the absence of air due to
 Continuous evolution of hydrogen at the cathode facilitating anodic oxidation of the
metal.
 Dissolution of the corrosion product (oxide layer) in acidic medium exposing fresh
metal surface for corrosion.
If the pH is above 10, corrosion practically stops due to the formation of a protective
coating. Between pH 3 and 10 corrosion occurs only in the presence of oxygen.
d) Temperature:

In general, increase in temperature increases rate of corrosion. This is due to

 Increase in temperature increases the conductance of the aqueous medium since ions
gain kinetic energy & move faster. Therefore, rate of corrosion increases.
 An increase in temperature decreases the passivity of metals & leads to corrosion of
passive metals such as Al, Cr etc.
 Increase in temperature, increases the solubility of corrosion product in the medium
and breaks the protective film that might exist on the surface. Therefore, rate of
corrosion increases.
e) Conductivity:

Presence of conducting species in the atmosphere increases the rate of corrosion. This is
because, higher the conductivity of the medium, faster the ions can migrate between anodic
and cathodic regions of the corrosion cell, in turn faster will be the exchange of electrons at
the electrode surfaces. Therefore, corrosion problem is more in the sea water than in
fresh water.

Types of Corrosion
1. Differential metal corrosion:
This is also known as galvanic corrosion. It occurs when two dissimilar metals are in
contact with each other in a corrosive conducting medium. The metal with lower standard
reduction potential acts as anode and gets oxidized and suffers from corrosion. The metal with
higher standard reduction potential acts as cathode and do not suffer from corrosion.

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Corrosion control & Electrode system BGSCET-2023

Example (a): Consider a bimetallic sample of iron and copper in fig (a). Iron (-0.44V) is
placed above copper (+0.34V) in the electrochemical series. Therefore, iron acts as anode and
undergoes corrosion, whereas copper acts as cathode and remains unaffected.
At anode: Fe Fe2+ + 2e-

At cathode: H2O + ½ O2 + 2e- 2OH–

Fe2+ + 2OH- Fe (OH)2

Example (b): Consider a bimetallic sample of iron and zinc in fig (b). Zinc (-0.76V) is
placed above iron (-0.44V) in the electrochemical series. Therefore, zinc acts as anode and
undergoes corrosion, whereas iron acts as cathode and remains unaffected.
At anode: Zn Zn2+ + 2e-
At cathode: H2O + ½ O2 + 2e- 2OH–
Zn2+ + 2OH- Zn (OH)2

2. Differential aeration corrosion:

Differential aeration corrosion occurs when two different parts of the same metal are
exposed to two different air concentration or oxygen concentration. Since cathodic reaction
requires O2, the part of the metal exposed to more air acts as cathode and part of the metal
less aerated acts as anode. So, a difference in potential is created which causes flow of
electrons between two differentially aerated areas of the same metal. Consequently, poorly
aerated region undergoes corrosion.

Example (i):

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Corrosion control & Electrode system BGSCET-2023

Consider a pure iron rod which is partially immersed in an aerated solution of NaCl.
Since cathodic reaction requires O2, the part of the iron rod exposed to air always acts as
cathode. The portion of the iron rod immersed in NaCl is act as an anode. Hence, electrons
flow from bottom to top of the rod. The reactions involved are as follows:

At anode: Fe Fe2+ + 2e-

At cathode: H2O + ½ O2 + 2e- 2OH–

Fe2+ + 2OH- Fe (OH)2

ii) Window rods inside the frame corrode more than the exposed region.
iii) Paper pins inside the paper get corroded and the other part is free from corrosion.

i) Water line corrosion:

This type of corrosion is an example of differential aeration corrosion. This is observed in

a) Water Storage Tank - in which water is stored for a long period.
b) Ocean going ship - hulls of ships which float for long periods in the sea water.
Corrosion of a metal just below the water line (water level) is referred to as water line
corrosion. The part of the metal below the waterline being less oxygenated acts as anode
and undergoes corrosion. The part of the metal above the waterline which is more
oxygenated acts as cathode and it is unaffected. Intense corrosion occurs at the anode and
reduction of oxygen occurs near the waterline. Hence it is called water line corrosion.

The reactions involved are as follows:

At anode: Fe Fe2+ + 2e-
At cathode: H2O + ½ O2 + 2e- 2OH–
Fe2+ + 2OH- Fe (OH)2
ii) Pitting corrosion:
This type of corrosion is an example of differential aeration corrosion. Pitting corrosion is a
localized and accelerated corrosion resulting in the formation of pit or cavity. Pitting
corrosion results when extraneous matter such as sand, dust particles, etc. are get deposited
on a metal surface. The metal portion below the extraneous matter will not be well

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Corrosion control & Electrode system BGSCET-2023

oxygenated compared to the other metal surface. Hence the covered metal surface acts as
anode and uncovered metal surface acts as cathode. In presence of a moisture, corrosion starts
below the extraneous matter. This causes pits or cavities in the metal. Hence it is called
pitting corrosion. Once a pit is formed the rate of corrosion increases. This is because of the
formation of small anodic area.

The reactions involved are as follows:

At anode: Fe Fe2+ + 2e-
At cathode: H2O + ½ O2 + 2e- 2OH–
Fe2+ + 2OH- Fe (OH)2
Example: (1) Less aerated part of the machinery.
(2) Less aerated parts of barbed wire.

Corrosion Control methods

Metallic coating:
Deposition of a protective metal over the surface of a base metal is called metallic coating.
Anodic Coating: Anodic coatings are produced by coating a base metal with more active
metals (having lower electrode potential) which are anodic to the base metal.
Galvanization is an example of anodic metal coating. Coating of Zn over iron as base metal
is called galvanization. Galvanization is carried out by hot dipping method.
The process involves the following steps:

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Corrosion control & Electrode system BGSCET-2023

1. The iron metal surface is first washed with organic solvents (benzene or toluene, etc.) to
remove oil, grease, etc.
2. Rust and other deposits are removed by washing with dilute sulphuric acid.
3. Finally, it is washed well with distilled water and dried using hot air.
4. The cleaned & dried iron metal is then dipped in bath of hot molten Zn at 420 – 430 ˚C
and the surface of the bath is kept covered with ammonium chloride as a flux to prevent
the oxidation of molten zinc. Ammonium chloride will also act as adherent for Zn coating.
5. When the iron metal is taken out, the excess Zn on the surface is removed by passing
through a pair of hot rollers, which wipes out excess of Zn coating and produces a thin
coating.
Applications:
1. Galvanized iron pipes are used for supplying potable water for domestic purpose.
2. Galvanized iron drums are used to preserve variety of chemicals, drugs and organic
solvents.
3. Zinc gets dissolved in dilute acids to form highly toxic compounds. Hence, galvanized
utensils are not used for storage of food products.

Anodizing:
Anodizing is a process of developing an oxide layer on the surface of metal by anodic
oxidation in an electrolytic cell. Metals such as Al, Ti, Mg, V and Zr are anodized in the
presence of electrolyte like chromic acid, sulphuric acid, oxalic acid or boric acid, by
electrochemical oxidation. This method is not applicable to ferrous and its alloys.
The process anodization of aluminium:

1. The Al article to be anodized is first de-greased with organic solvents and polished to get
clean surface. It is used as anode.
2. Pb is generally used as cathode.

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Corrosion control & Electrode system BGSCET-2023

3. Both the electrodes are dipped in the 5-10% chromic acid electrolytic solution. The
electrolysis is carried out by passing D.C voltage of 40V at 35-40 ˚C.
4. A thin oxide layer of aluminium (Al2O3) of 5-20 nm thickness is formed on the anode.
This oxide layer is slightly porous.
Anode: 2Al + 3H2O Al2O3+ 6H+ + 6e-
Cathode: 6H+ + 6e- 3H2
Overall reaction: 2Al + 3H2O Al2O3+3H2
5. The strength of oxide layer formed is increased by dipping in boiling water. This treatment
changes the porous surface into a sealed surface by forming monohydrate of aluminium
oxide (Al2O3.H2O).

Application:
1. Anodized aluminium is used in manufacture of pressure cookers, aircrafts & window
frames.
2. Anodized aluminium is used in office partitions.
Cathodic protection:
The principle involved in this method is to force the metal to be protected to behave as
cathode, there by corrosion does not occur. This phenomenon is known as cathodic
protection. There are two methods.
a) Sacrificial anode method:
 In this method, base metal is converted into cathode by connecting it to more active
metals.
 These active metal acts as auxiliary anodes. Zn, Mg and Al are the common auxiliary
anodes used in this method.
 The anodic metal being more reactive undergo corrosion and gives the electrons to the
base metal and forces it to act as cathode, which remains unaffected.
 The sacrificial anodes have to be replaced from time to time after complete corrosion.
 Since the anodic metals are sacrificed to protect the base metal, the method is
known as sacrificial anode method.

Application:
1. It is used for protecting underground steel tanks with Mg blocks.

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Corrosion control & Electrode system BGSCET-2023

2. Mg bars are fixed to the sides of ocean-going ships to act as sacrificial anodes.
3. It is used for protecting buried iron pipe lines with Mg blocks.

a) The presence of dust particles on iron surface for a long period.

This is due to pitting corrosion. Pitting corrosion results when small particles of dust
are get deposited on a metal. The portion covered by the dust will not be well oxygenated
compared to the exposed surface. Hence the covered surface becomes anodic with respect to
the surface exposed. In presence of a moisture corrosion starts below the dust part. This
causes pits or cavities in the metal. The reactions involved are as follows:
At anode: Fe Fe2+ + 2e-

At cathode: H2O + ½ O2 + 2e- 2OH–

Fe2+ + 2OH- Fe (OH)2

b) Steel pipe connected to copper plumbing.

This is due to galvanic corrosion. Iron or steel is placed above copper in the electrochemical
series. Therefore, iron acts as anode and undergoes corrosion, whereas copper acts as
cathode and remains unaffected. The reactions involved are as follows:
At anode: Fe Fe2+ + 2e-
At cathode: H2O + ½ O2 + 2e- 2OH–
Fe2+ + 2OH- Fe (OH)2

Corrosion Penetration Rate (CPR):

Corrosion Penetration Rate (CPR) is defined as: The speed at which any metal in a specific
environment deteriorates due to a chemical reaction in the metal when it is exposed to a
corrosive environment.

W = Weight loss, mg
ρ = density of specimen, g/cm3
A = area of specimen, sq. in.
t = exposure time, hr
K is constant depends on unit used, when K = 534 the unit mpy will be used.
When K = 87.6, the unit mm/yr. will be used.
CPR<20 mil/yr. or about 0.5 mm/yr. is acceptable

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Corrosion control & Electrode system BGSCET-2023

NUMERICAL PROBLEMS
Problem 1: A piece of corroded steel plate was found in a submerged ocean vessel. It was
estimated that the original area of the plate was 10 in2 and that approximately 2.6 kg had
corroded away during the submersion. Assuming a corrosion penetration rate of 200 mpy for
this alloy in sea water, estimate the time of submersion in years. The density of the steel is
7.9 g/cm3.

Solution: Given: CPR= 200 mpy, W= 2.6 kg, A= 10 in2,  = 7.9 g/cm3
KW
CPR=
ρAt
534x 2.6
200 = x 106 [1kg = 106 mg]
7.9 x 10 x t
534x 2.6
t = x 106
7.9 x 10 x 200
87,893
t = hrs
8760
= approx. 10 years. [1yr = 24 hr x 365 days = 8760 hrs]
Problem 2: A metal iron plate was found in a vessel containing acidic media, it was
estimated that the original area was 20 inch2 that approximately 1.2 kg had corroded.
Assuming a corrosion penetration rate of 400mpy for this iron in acidic, calculate time in
years, density of iron 7.87g/ cm3.
Solution:
A = 20in2 W = 1.2kg = 1.2 x106mg CPR=400mpy ρ = 7.87g/cm3

KW
CPR=
ρAt

534 X 1.2 x 106

400 =
7.87 X 20 X t

534 X 1.2 x 106

t=
7.87 X 20 X 400

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Corrosion control & Electrode system BGSCET-2023

640.8 x 106
t= = 10,177.89 hrs [1yr = 24 hr x 365 days = 8760 hrs]
62,960

10,177.89
t= = 1.16yrs
8,760

Problem 3: A thick steel sheet of area 400cm2 is exposed to air near the ocean. After a one-
year period it was found to experience a weight loss of 375g due to corrosion. To what rate of
corrosion, in both mpy and mm/yr., does this correspond? The density of the steel is
7.9g/cm3.
Solution: A= 400 x 0.155 = 62 in2 1 cm2 = 0.155 in2
KW
CPR=
ρAt
534x 375
CPR = x 103 = 46.7 mpy.
7.9 x 62 x 365 x 24
87.6 x 375
CPR = x 103 = 1.19 mm/yr.
7.9 x 400 x 365 x 24
Problem 4: A thick metal plate of area 40 in2 has corroded in ocean belt. If the corrosion rate
is 295mpy. Calculate its density if the weight lost due to corrosion is 5.8kg after 2 years.
Solution:
KW
CPR=
ρAt
534x 5.8
295 = x 106
ρ x 40 x2 x 365 x 24
534x 5.8
ρ= x 106= 14.98 g/cm3
295 x 40 x 2 x 365 x 24

Problem 5: A metal bar of area 25in2 has been left inside an ocean belt for 4 years. If the
corrosion penetration rate is 45.8 mpy. Calculate the weight lost, if density of the metal is
7.9g/cm3.
Solution:
KW
CPR=
ρAt

534x W
45.8 =
7.9 x 25 x 4 x 365 x 24
45.8 x 7.9 x 25 x 4 x 365 x 24
W= = 593547 mg = 0.593 kg
534

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Corrosion control & Electrode system BGSCET-2023

Problem 6: Calculate the CPR of the metal in mm/yr. whose area exposed in sea water for 12
years is 123cm2. Density of the metal was found to be 12.4g/cm3 and weight lost by the metal
is 3kg.
Solution:
KW
CPR=
ρAt
87.6 x 3
CPR = x 106= 1.639 mm/yr.
12.4x 123 x 12 x 365 x 24

Problem 7: Determine the area of the metal if its density 14.92 g/cm3 has lost 8.1kg in 3years
at a CPR 295mpy.
Solution:
KW
CPR=
ρAt
534 x 8.1
295 = x 106
14.92 x A x 3 x 365 x 24
534x 8.1
A= x 106 = 37.39 in2
14.92 x 295 x 3 x 365 x 24

Problem 8: 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=7.8 g/cm3)
Solution:
W = 40g = 40x103mg ρ = 7.8g/cm3 t = 6 x 30 x 24hrs

CPR in mmpy: K = 87.6 A = 1m x 3m = 3 m2 = 3x104 [1m=100cm]

KW
CPR=
ρAt

87.6 X 40 X 103
CPR =
7.8 X 3 X 104 X 6 X 30 X 24
3,504
CPR = X 10-1 = 0.00346 mm/yr = 3.466 X10-3 mmpy
1,01,088

CPR in mpy: K=534 A = 1m x 3m = 3 m2 = 3x1550 in2 [1m2=1550in2]

KW
CPR=
ρAt

534 X 40 X 103
CPR =
7.8 X 3 X 1550 X 6 X 30 X 24

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Corrosion control & Electrode system BGSCET-2023

21,360
CPR = X 103 = 0.1363 mpy
15,66,86,400

Problem 9: Calculate the CPR in both mpy and mmpy for a thick steel sheet of area 100 in2
which experiences a weight loss of 485 g after one year. (Density of steel=7.9g/cm3).
Solution:
W = 485g = 485 x 103mg t= 24x365 ρ = 7.9g/cm3

CPR in mm/yr : K = 87.6 A= 100in2 = 645cm2 [1 inch2= 6.45 cm2]

KW
CPR=
ρAt

87.6 X 485 x 103

CPR =
7.9 X 645 X 365X 24

42,486 X103
CPR = = 0.9518 mm/yr
4,46,36,580

CPR in mpy: K = 534 A = 100 in2

KW
CPR=
ρAt

534 X 485 x 103

CPR =
7.9 X 100 X 365X 24

2,58,990 X103
CPR = = 37.4241 mpy
69,20,400

Problem 10: A thickness of brass sheet of area 400 inch2 is exposed to air near the ocean.
After two years period it was found to experience a weight loss of 375g due to corrosion. If
the density of Brass is 8.73 g/cm3. Calculate the CPR in mm/year and mpy
Solution:
W = 375g = 375x103mg t = 2yrs ρ = 8.73g/cm3
CPR in mm/yr: K = 87.6 A = 400 in2 = 400 x 6.45 cm2 [1 inch2= 6.45 cm2]

KW
CPR=
ρAt

87.6 X 375 x 103

CPR =
8.73 X 400 X 6.45 X 2 X 365X 24

32850 X103
CPR = = 0.0832 mm/yr
39,46,09,968

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Corrosion control & Electrode system BGSCET-2023

CPR in mpy: K = 534 A = 400 in2

KW
CPR=
ρAt

534 X 375 x 103

CPR =
8.73 X 400 X 2 X 365X 24

2,00,250 X103
CPR = = 3.2731 mpy
6,11,79,840

ADDITIONAL NUMERICAL PROBLEMS

Problem 11: A piece of corroded aluminium plate was found in a submerged ocean vessel; it
was estimated that the original area was 64cm2 that approximately 350 g had corroded away
during the submersion. Assuming a corrosion penetration rate of 2.4 mmy for this alloy in sea
water, estimate the time in years, density of aluminium 2.7 g/ cm3 [ Ans: t = 8.44 yrs].

Problem 13: A metal iron plate was found in a vessel containing acidic media, it was
estimated that the original area was 20 inch2 that approximately 1.2 kg had corroded.
Assuming a corrosion penetration rate of 400mpy for this iron in acidic, calculate time in
years, density of iron 7.87g/ cm3. [t = 1.16yrs]
Problem 14: A thickness of alloy sheet of area 100 inch2 is exposed to air near the ocean.
After 1 year period it was found to experience a weight loss of 35 g due to corrosion. If the
density of alloy is 8.4 g/cm3. Calculate the CPR in mmy and mpy. [Ans: 0.064mmpy &
2.54mpy]

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Corrosion control & Electrode system BGSCET-2023

Electrode System
Types of electrodes:
1) Metal-Metal ion electrodes: These are the electrodes where a metal is
dipped in solution containing its own ions. Eg: Cu|CuSO4, Zn|ZnSO4
2) Gas electrodes: These are the electrodes where gas is in contact with an inert
metal like platinum dipped in an ionic solution of gas molecules. Eg: Hydrogen
electrode.
3) Metal–Metal insoluble salt electrodes: These are the electrodes where a metal
will be in contact with its insoluble salt. Eg: Calomel electrode (Hg|Hg2Cl2|Cl-),
Silver-Silver chloride electrode (Ag|AgCl|Cl-).
4) Ion selective electrodes: These are the electrodes which are sensitive to
particular ionic species and will develop a potential when a membrane is in
contact with an ionic solution. Eg: Glass electrode
5) Redox electrodes: These are the electrodes, where inert metal like Pt will be in
contact with oxidized and reduced species of the same metal in solution. Eg:
Pt|Fe2+, Fe3+and Pt|Sn2+, Sn4+
6) Amalgam electrodes: An amalgam electrode is a modification of metal-
metal ion electrode. These are electrodes in which metal amalgam is dipped in the
solution of its own metal ions. Eg: Lead amalgam electrode (Pb-Hg/Pb2+)

Ion selective electrodes:

These are the electrodes which are sensitive to particular ionic species and will develop a
potential when a membrane is in contact with an ionic solution.
Example: Glass electrode
Glass electrode is an ion selective electrode in which a thin glass membrane is present which
is permeable to H+ ion and not to other ions in the solution.
Construction:
 A glass electrode consists of a thick–walled glass tube with a very thin walled glass
membrane (bulb) at the bottom. Its thickness varies from 0.01-0.03 mm.
 This glass membrane made up of special glass of low melting point and high electrical
conductivity. The approximate composition of this glass is 72% SiO2, 22% Na2O and 6%
CaO.
 This glass membrane allows only H+ ions up to a pH range from 1 to 9.
 The glass bulb is filled with 0.1M HCl in which a silver–silver chloride electrode is dipped
as an internal reference electrode which provides external electrical contact.
Representation: Ag|AgCl|HCl(0.1M) |glass membrane

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Corrosion control & Electrode system BGSCET-2023

Working:
When the glass electrode is dipped in the test solution, the Na+ ions of the glass membranes
are exchanged for H+ ions of the test solution.
Na+Gl- + H+ H+Gl- + Na+
Membrane Solution Membrane Solution

When a glass electrode is placed between two H+ ion solutions of different concentrations
(C1 and C2), boundary potential is developed across the membrane. The boundary potential
is given by the equation.

𝟎. 𝟎𝟓𝟗𝟏 𝑪𝟐
𝑬𝒃 = 𝒍𝒐𝒈
𝒏 𝑪𝟏

0.0591 0.0591
Eb = log C2 – log C1 (n=1 for H+ ion)
n n

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Corrosion control & Electrode system BGSCET-2023

Eb = 0.0591 logC2 – 0.0591 logC1

Eb = L + 0.0591logC2
(Where L = - 0.0591logC1, is a constant, ∵ C1 = 0.1M)
Since C2 is the unknown H+ concentration, we can write
Eb = L + 0.0591 log[H+] (since pH = - log [H+])

Eb = L - 0.0591pH ……………………..(1)
It is found that the potential of the glass electrode (EG) has three components:
 Boundary potential (Eb)
 Asymmetric potential (Eassy)
 Potential of the internal reference Ag – AgCl electrodes (EAg/AgCl)

∴ EG = Eb + Eassy + EAg/AgCl…………………….(2)

Substitute equation (1) in (2), we get

EG= (L- 0.0591 pH) + Eassy + EAg/AgCl
EG = E0G – 0.0591pH
Where E0G = L+ Eassy + EAg/AgCl . E0G is the combination of three constant terms.

Determination of pH of solution using glass electrode

The cell consists of a glass electrode as indicator electrode and a saturated calomel electrode
(SCE) as reference electrode, the cell is immersed in a solution whose pH is to be determined.
The emf cell is measured using vacuum tube voltmeter (VTVM).

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Corrosion control & Electrode system BGSCET-2023

The cell assembly is represented as:

Pt|Hg|Hg2Cl2 |KCl(sat)||solution of unknown pH| glass membrane|HCl (0.1M) |AgCl|Ag
The emf of the cell is given by
Ecell = Ecathode – Eanode
Ecell = EG – ESCE
E cell = (E0G – 0.0591 pH) – ESCE (Where EG =E0G – 0.0591 pH)

𝑯
𝑬𝟎𝑮 − 𝑬𝒄𝒆𝒍𝒍 − 𝑬𝑺𝑪𝑬
𝒑 =
𝟎. 𝟎𝟓𝟗𝟏

E0G value of a glass electrode can be determined by using a solution of known pH.

Advantages and disadvantages of glass electrodes.

Advantages:
 Glass electrodes are portable and easy to operate.
 Accurate results are obtained between pH ranges 1 – 9. However, by using special glass
electrodes the range can be extended to 1 – 14.
 It is not easily poisoned.
 It can be used even in presence of oxidizing and reducing agents.
 Equilibrium is rapidly achieved.
 It can be used for coloured, turbid and colloidal solutions.
 It does not require the use of any salt bridge.

Disadvantages:
 Glass electrode cannot be used in presence of fluoride ions since they attack the glass
membrane.
 Glass electrodes are very thin and fragile, should be handled with care.
 It requires special glass membrane for solutions of pH more than 9.
 Glass membrane has high internal resistance; ordinary potentiometer is not employed
and hence requires vacuum tube voltmeter (VTVM). This is relatively costlier when
compared to ordinary potentiometer.

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Corrosion control & Electrode system BGSCET-2023

Reference electrodes: These are the electrodes of constant potential which are used to
determine electrode potential of other electrodes. There are two types of reference electrodes.
 Primary reference electrode. Eg: Standard hydrogen electrode.
 Secondary reference electrode. Eg: Calomel electrode, Ion selective electrode.
Construction and working of calomel electrode:
Construction:

 Calom el electrode is a metal- metal insoluble salt electrode and is a secondary

reference electrode.
 Calomel electrode consists of a glass tube. A small amount of pure mercury is placed
at the bottom of the glass tube and it is covered by a paste of Hg and calomel
(mercurous chloride).
 The remaining portion of the glass tube is filled with KCl solution of known
concentration (saturated, 1N or 0.1N).
 A platinum wire is dipped into the mercury and is used to provide external electrical
contact. The porous plug at the bottom acts as a salt bridge.
 Representation: Pt|Hg|Hg2Cl2|KCl(x) Where x = sat or 0.1N or 1N.
Working: Calomel Electrode can act as anode or cathode depending on the nature of the
other electrode.
At anode: 2Hg + 2Cl- Hg2Cl2 + 2e-
At cathode: Hg2Cl2 + 2e- 2Hg + 2Cl-
At equilibrium: Hg2Cl2 + 2e- 2Hg + 2Cl-
The electrode potential is given by
Ecal= E0 – 0.0591 log [Cl-]
From the above equation it is clear that as the concentration of Cl- ion increases, the electrode
potential decreases.

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Corrosion control & Electrode system BGSCET-2023

Advantages:
 It is easy to construct and maintain.
 Its potential can remain constant and it can easily be reproduced.
 It can be used in the presence of oxidizing agents.
Applications:
 It is used as reference electrode in all potentiometric titrations.
 It is used as reference electrode with glass electrode in pH determination.
 It is used as a secondary reference electrode in the measurement of single electrode
potential.
Note: At 298K, the electrode potentials are as follows.
KCl concentration 0.1N 1N Saturated
Ecal (V) 0.334 0.281 0.2422

Electrolyte concentration cells: The galvanic cell in which electrode and

electrolyte present in both half cells are same but only the concentration of electrolyte is
different is called electrolyte concentration cell.

Derivation:

The above concentration cell can be represented as:

Zn| ZnSO4(C1) || ZnSO4(C2)| Zn
The electrode reactions are
At anode: Zn Zn2+ (C1) + 2e-
At cathode: Zn2+(C2) +2e- Zn
2+ 2+
NCR: Zn (C2) Zn (C1)

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 Corrosion control & Electrode system BGSCET-2023

Where C1 and C2 are concentrations of ZnSO4 solution at anode and cathode

respectively & C2 > C1
2.303RT
Emf of anode is given as: Eanode= E0(Zn2+/Zn)+ log C1 ……………….(1)
nF
2.303RT
Emf of cathode is given as: Ecathode= E0(Zn2+/Zn)+ log C2 …………….(2)
nF
Ecell = Ecathode – Eanode…………..(3)
Substitute eqn (1) & (2) in (3),
2.303RT 2.303RT
Ecell= (E0(Zn2+/Zn)+ log C2) – (E0(Zn2+/Zn)+ log C1)
nF nF
2.303RT 2.303RT
Ecell= log C2 – log C1
nF nF
2.303RT
Ecell= (log C2 – log C1)
nF
2.303RT C2
Ecell = log
nF C1

On substituting the values for R = 8.314 J/K/mol, T = 298K & F = 96500 C

0.0591 C2
Ecell = log
n C1

Numerical Problems
[1] A concentration cell was constructed by immersing two silver electrodes in 0.02M and
2M AgNO3 solutions. Write the cell representation, cell reactions and calculate the emf
of the cell at 25 ˚C.
Solution:
(i) Cell representation: Ag|AgNO3(0.02 M) || AgNO3(2M)|Ag
(ii) Electrode reactions: At anode: Ag Ag+(0.02M) + e-
At cathode: Ag+(2M) + e- Ag
NCR: Ag+(2M) Ag+(0.02M)
(iii) The emf of the concentration cell:
0.0591 C2
Ecell = log
n C1

0.0591 2
Ecell = log
1 0.02
Ecell = 0.0591 log(100)
Ecell = 0.0591 X 2
Ecell = 0.1182 V

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 Corrosion control & Electrode system BGSCET-2023

[2] Represent the cell formed by the coupling of two Cu electrodes immersed in CuSO4
solutions. The concentration of cupric ions in one electrode system is 100 times more
concentrated than other. Write the cell reaction and calculate the potential at 300 K.

Solution:
(i)Cell representation: Cu|CuSO4(x M) || CuSO4(100x M)|Cu
(ii) Electrode reactions: At anode: Cu Cu2+(x M) + 2e-
At cathode: Cu2+(100x M) +2e- Cu
NCR: Cu2+(100x M) Cu2+(x M)
(iii)The emf of the concentration cell:
2.303 RT C2
Ecell = log
nF C1

2.303 x 8.303 x 300 100

Ecell = log
2x96500 1
Ecell = 0.0297 log(100)
Ecell = 0.0297 X 2
Ecell = 0.0595 V

[3] A cell is obtained by combining two Cd electrodes immersed in cadmium sulphate

solutions of 0.1M and 0.5M at 25 oC. Write the cell representation, cell reactions and
calculate the emf of the concentration cell.
Solution:
(i) Cell representation: Cd|CdSO4(0.1 M) || CdSO4(0.5 M)|Cd
(ii) Electrode reactions: At anode: Cd Cd2+(0.1 M) + 2e-
At cathode: Cd2+(0.5 M) +2e- Cd
NCR: Cd2+(0.5 M) Cd2+(0.1 M)
(iii) The emf of the concentration cell:
0.0591 C2
Ecell = log
n C1

0.0591 0.5
Ecell = log
2 0.1
Ecell = 0.02955 log(5)
Ecell = 0.02955 X 0.6989
Ecell = 0.0207 V

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 Corrosion control & Electrode system BGSCET-2023

[4] The emf of the cell Cu| CuSO4(0.01 M) ||CuSO4(x M) | Cu is 0.0295V at 25 oC. Find the
value of x.
Solution:
0.0591 C2
The emf of the concentration cell: Ecell = log
n C1

0.0591 x
0.0295 = log
2 0.01
x
log0.01 = 0.9983
log(x) – log(0.01) = 0.9983
log(x) – (-2) = 0.9983
log(x)+2 = 0.9983
log(x) = 0.9983-2
log(x) = -1.0017
x = antilog (-1.0017)
x= 0.0996 M

[5] A spontaneous galvanic cell tin|tin ion (0.024M)||tin ion (0.064M)|tin develops an emf of
0.0126V at 250C. Calculate the valency of tin.

Solution:
0.0591 C2
The emf of the concentration cell: Ecell = log
n C1

0.0591 0.064
0.0126 = log
n 0.024

0.0591 0.064
n = 0.0126 log
0.024

n=4.690xlog(2.6666)
n=1.99 ≈ 2 (n is the valency of tin)

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Corrosion control & Electrode system BGSCET-2023

Analytical Techniques
Potentiometry
Potentiometry is the estimation of substances in solution by observing sudden change in
potential of the cell at equivalence point.

Theory: The relation between electrode potential and metal ion concentration is given by the
Nernst equation.
0.0591
E = Eo+ log[Mn+]
n

The potential of an electrode E depends upon the concentration of the ion Mn+ to which it is
reversible.

Assume the concentration of the analyte to be x mol/dm3. Let y mol/dm3 be the volume of
titrant added at a given instant. Under these conditions let z mole of the product be formed.
The value of z will vary through the course of the titration since the concentration of the
titrant is being continuously altered.

Initially the change in potential will be small. At the equivalence point, there will be sharp
raise in the potential. Beyond the equivalence point, there will be small change in the
potential. The equivalence point can be determined by plotting ∆E/∆V against volume of the
titrant added.

Instrumentation: A potentiometer consists of a reference electrode, an indicator 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 simple
arrangement of potentiometric titration is shown in Figure.

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Corrosion control & Electrode system BGSCET-2023

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 0.5ml and
the potential is measured each time. The end point is determined by plotting change in
potentials against the volume of titrant.
Applications:

1. It is used in redox titrations to estimate the concentration of analyte in the sample

solution. Example: Estimation of FAS potentiometrically using standard K2Cr2O7
solution.
2. It is used in precipitation titrations, which involves insoluble salt metals. Example:
Titration of silver ion with a halide ion. Silver electrode is used as indicator electrode.

Conductometric titration
Theory: Ohm’s law states that the current I (ampere) flowing through a conductor is directly
proportional to the applied potential, E (volt) and inversely proportional to the resistance R
(ohms) of the conductor.

𝐸
I=
𝑅

The reciprocal of the resistance is called conductance. The resistance of a homogenous

material of uniform cross section with an area of ‘A’ sq. cm and length ‘l’ cm is given by

𝜌𝑋𝑙
R=
𝐴

Where ρ is specific resistance or resistivity.

The reciprocal of the specific resistance is called specific conductance (κ). Specific
conductance of an electrolyte solution is the conductance of the solution present between two
parallel electrodes of 1cm2 area of cross section and 1cm apart.

The specific conductance of the solution is given by

1 𝑙
k= X
𝑅 𝐴

l/A is known as the cell constant and R is the resistance of the solution.

Conductance measurements are used to determine the equivalence point in acid – base
titrations. There is a sudden change in conductance of the solution after the equivalence point.

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Corrosion control & Electrode system BGSCET-2023

The equivalence point is determined graphically by plotting conductance against the volume
of titrant added.

Instrumentation: A simple arrangement of conductometric titration is shown in Figure. It

consists of two platinum electrodes each of unit area of cross section placed unit distance
apart. The electrodes are dipped in the electrolytic solution taken in a beaker. It is connected
to a conductivity bridge. 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. 5ml.The end point is
determined by plotting conductance against the volume of titrant added.

Application:

Explain the nature of conductometric graph for the following titrations

a) Strong acid with a strong base:

Consider the titration of HCl against NaOH.

NaOH + HCl NaCl + H2O

The conductance initially decreases till complete neutralization of the HCl takes place. This is
due to the replacement of highly mobile H+ ion by the Na+ ion. After complete neutralization
of the HCl, further addition of NaOH raises the conductance sharply. This is due to increase in
the concentration of the OH- ions. A plot of conductance (ohm-1) against the volume of NaOH
(cm3) gives a graph as shown in Figure. The point of intersection of the curve gives the
equivalence point.

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Corrosion control & Electrode system BGSCET-2023

b) Weak acid with strong base:

Consider the titration of acetic acid against NaOH.

CH3COOH + NaOH CH3COONa + H2O

The conductance will be initially low since acetic acid is a weak electrolyte. When NaOH is
added to the acetic acid, the sodium acetate formed is highly ionized and the conductance
increases. After complete neutralization of the acetic acid, further addition of NaOH raises the
conductance sharply. A plot of conductance (ohm-1) against the volume of NaOH (cm3) gives
a graph as shown in Figure. The point of intersection of the lines gives the equivalence point.

c) Mixture of acids (strong and weak) with strong base:

Consider the titration of mixture of HCl and acetic acid against

HCl + NaOH NaCl + H2O

CH3COOH + NaOH CH3COONa + H2O

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Corrosion control & Electrode system BGSCET-2023

HCl being stronger acid than CH3COOH will get titrated first. The titration of
CH3COOH will start only after HCl is completely neutralized.
During the titration of HCl verses NaOH, the conductivity decrease due to
+ +
replacement of H ions with Na ions. After neutralization of HCl, the neutralization of
CH3COOH will start and the conductivity increases to small extent till its neutralization is
complete due to the sodium acetate formed is highly ionized. After neutralization of
CH3COOH, the conductance rapidly rises with further additions of NaOH. This is due to
increase in the concentration of the OH- ions. A plot of conductance (ohm-1) against the
volume of NaOH (cm3) gives a graph as shown in Figure. The point of intersection of the
lines gives the equivalence point V1 and V2.

********************

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