Corrosion and Electrode System

“Corrosion is defined as the destruction or deterioration of metals or alloys by the

surrounding environment through chemical or electrochemical reactions”.
Corrosion may occur either in dry environment or in an aqueous medium.
Dry Corrosion (Chemical Corrosion): Dry corrosion occurs by direct attack of atmospheric
gases such as oxygen, hydrogen sulfide, halogens, and sulfur dioxide on the metal forming
oxide layer.
Wet Corrosion (Electrochemical Corrosion): Wet corrosion occurs in presence of an
aqueous solution of electrolyte & atmospheric oxygen by setting up of tiny galvanic cells on
the metal surface.
Electrochemical Theory of Corrosion
According to this theory, when a metal is exposed to the atmosphere following
electrochemical changes occur.

i) Formation of Anodic & Cathodic sites takes place leading to formation of tiny
galvanic cells. The electrons are liberated at anodic site & are taken up by the
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cathodic site.
ii) The metal dissolves at the anodic site (oxidation) i.e. corrosion takes place at
the anodic site.
iii) Reduction of H2O & O2 to OH– & H2 occurs at the cathodic site.

Electrochemical theory of corrosion is explained by exposing Iron to the atmosphere. When a

small piece of Iron metal is exposed to the atmosphere, formation of Anodic and Cathodic
sites takes place on the surface of Iron and following electrochemical changes occur.
At Anode
Oxidation of Fe takes place resulting in corrosion.

Fe Fe2+ + 2e – oxidation.
At Cathode
The electrons liberated at anode flow to the cathode & cause reduction of H 2O & O2 at the
cathode. The reduction process depends on the nature of electrolyte i.e. atmospheric moisture
or water film.
a) If the moisture or water film is aerated & neutral.

O2 & H2 O reduce to OH – ions.

2 H2 O + O2 + 4e– 4 OH –

b) If the moisture or water film is deaerated & neutral.

H2O reduces liberating H2 gas & OH – .

2 H2 O + 2e– H2 + 2 OH–

c) If the moisture or water film is deaerated & acidic.

Atmosphere (H2 O + O2)
H+ ions reduce to H2 gas.
2 H+ + 2e– H2
Anodic Area Cathodic Area

Page 1 of 27
 The Fe2+ & OH– ions combine to form the corrosion product, which settles down between the
anodic and cathodic sites.
Fe2+ + 2 OH– Fe (OH)2 - Iron Hydroxide

Further Fe (OH) 2 oxidizes to hydrated Ferric oxide.

4 Fe (OH)2 + 2 H2 O + O2 2 (Fe2 O3. 3H2O) Rust

Types of Corrosion
1. Differential metal corrosion.
2. Differential aeration corrosion.
1. Differential Metal Corrosion.
When two dissimilar metals are in contact, potential difference arises due to the formation
of tiny galvanic cells & corrosion occurs at the anode. A metal placed high in the
electrochemical series acts as anode & the other metal acts as cathode.
Thus Iron (Fe) is anode to Sn, Cu, Ni and hence Iron (Fe) undergoes corrosion. On the other
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hand Fe acts as a cathode to Mg & Zn, as a result, Mg & Zn undergo corrosion in presence of
Fe.
e e
e.g.

Fe Cu Fe Zn

In this bimetallic couple Iron as anode undergoes corrosion & Copper as cathode is protected.
This is because Iron is above Copper in the galvanic series.

If Fe is coupled with Zn, Zinc as anode gets corroded & Fe as cathode is protected. This is
because Zn is above the Iron in galvanic series.

The rate of corrosion depends on the amount of current passing from cathode to anode.
Higher the difference in the reduction potentials of two metals; higher is the rate of corrosion.
For instance potential difference between Fe & Cu is more than that of between Fe & Sn.
Therefore Fe corrodes faster in presence of Cu than in presence of Sn.

“In general in a bimetallic couple, the metal which is more anodic gets corroded & the
other metal which becomes cathode is protected”. Hence, Bolt and nuts are always made
of similar metal.

2. Differential aeration corrosion.

The difference in concentration of Oxygen over the surface of a metal develops galvanic
cell resulting in corrosion. The metal surface where the concentration of O 2 is high becomes
cathode, since cathodic reactions involve the reduction of O 2 and the surface where the
concentration of O2 is less becomes anode.

Consider a strip of pure Fe is partially immersed vertically in a solution of aerated NaCl. The
concentration of O2 is higher at the surface of the solution and cathodic reaction involves the
Page 2 of 27
 reduction O2 hence the upper portion of the strip becomes cathode. Whereas the concentration
of Oxygen is less at the lower portion & it becomes anode. The oxidation of metal i.e.
corrosion occurs at lower portion of the Fe strip immersed in NaCl and electrons pass from
bottom to the top of the strip and reduction of H 2O & O2 occur at upper portion of Fe strip .
The corrosion product is formed in between anodic & cathodic sites & not on active electrode
surface.

Fe Fe2+ + 2e– – Anodic reaction – at bottom.

O2 + 2H2 O + 4e– 4OH – – Cathodic reaction – at top.

Therefore well-aerated region of the metal becomes cathode & less aerated region becomes
anode, resulting in corrosion. This is known as differential aeration corrosion.
Fe O2
Cathode
2H2O + O2 +4e 4 OH –
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Aerated NaCl
Anode
Fe2+

This phenomenon of deferential aeration corrosion explains

a) Water line corrosion. b) Pitting corrosion.

a) Water line Corrosion

When water is stored in Iron tanks, it is generally found that the maximum amount of
corrosion takes place just below the water level. The area above the water line is highly
oxygenated acts as cathode & is protected. The area just below the water line becomes
anode & intense corrosion occurs. This is termed as water line corrosion.
This type of corrosion is observed in ships floating in seawater and water storage tanks.

b) Pitting Corrosion
When a large drop of water or an electrolyte or dust particles is placed on the surface of a
clean sheet of Iron, the concentration of O2 will be less at the bottom of the drop &
becomes anode, while O2 will be more at the surface area & becomes cathode. Hence
corrosion starts at the bottom of the drop causing pits or cavities at the bottom.

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 Corrosion Control
The total system in the universe is dynamic in nature and every metal always try to attain a
more stable state. In this process metals undergo corrosion through electrochemical reactions.
Corrosion cannot be totally prevented but it can be controlled effectively by various
techniques.

Anodizing
1. Surface Conversion coatings
Phosphating

Anodic metal coating (Galvanizing)

2. Metal coating
Cathodic metal coating (Tinning)

Sacrificial Anodic Method

3. Cathodic Protection
Impressed Current Method
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1. Inorganic Coatings
Anodizing:
When metals like Al, Ti, Cr, Vanadium, Zirconium etc. are made as anode in presence of
chromic acid, H2SO4, oxalic acid or phosphoric acid, a thin layer of oxide is formed, which
acts as a protective layer.

“Anodizing is an electrochemical process in which aluminium metal surface is

converted into a decorative, durable, corrosion resistance surface by formation of
passive oxide layer”.

Anodizing of Aluminum:
The aluminium metal object surface is degreased & polished. Aluminium metal object
is made as anode & platinum electrode as cathode in 3 – 10% chromic acid at 350C by
passing a current density of 10-20 mA/Cm2. A thin oxide layer (Al 2O3) of 2 – 8 microns
thickness is formed. The higher thickness can be obtained by addition of 10% H2 SO4 &
maintaining current density of 160 mA /cm2 which gives 24-micron thickness. The
aluminium object is dipped in aqueous solution of dye at 50 – 600C which gives colour.
Finally the object is treated with Ni & Co acetate followed by boiling water to improve
corrosion resistance.
Applications: - In Air crafts, window frames and utensils to provide corrosion resistance.

Page 4 of 27
 2. Metallic Coatings -Anodic Metal Coatings.
Iron is most commonly used metal & also the most susceptible to corrosion. In anodic
metal coating a base metal (Fe) is coated with more anodic metal in the electrochemical series
to protect the base metal (Fe) from corrosion, so that more anodic metals like Mg, Zn, Al &
Cd undergo corrosion protecting the base metal (Fe). Anodic metal coating is done by
the following method.
Galvanizing (Hot dipping)
It is a typical case of hot dip process in which Iron or steel sheets are coated with thin
film of Zn to prevent corrosion and are referred as G I Sheets. In this process Iron or steel
sheets to be coated are degreased using organic solvents. It is then treated with hot dilute
H2SO4 (800C) to remove any oxide layer and dipped in mixture of ZnCl 2 and NH4Cl and
dried. The finally the sheets are dipped in molten Zinc (430 – 470 0C). The sheets are cooled
& passed through hot rollers to get uniform thin layer of Zinc.
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Applications: Iron sheets coated with Zn are used for roofing and are referred commercially
as G I Sheets.
3. Cathodic Protection
In cathodic Protection, metal to be protected is made to remain as cathode always by
supplying electrons from an external source.
Corrosion occurs at anode due to oxidation of metal and flow of electrons from the anodic
area to cathodic area. At cathode reduction of H 2O & O2 occur and metal is protected at
cathode. Cathodic protection can be done by supplying electrons from external source to the
metal to be protected and making the metal to be protected remain as cathode always thereby
by protecting the metal.
The technique of providing electrons from an external source, and preventing the corrosion is
called Cathodic Protection. There are two types of cathodic protection.
i ) Sacrificial Anodic Method
In this method the metal to be protected is made as cathode by connecting insulated
copper wire to more anodic metal. More anodic metal undergoes corrosion by supplying
electrons to the cathodic metal thereby protecting the cathodic metal. Therefore this is called
as sacrificial anode method.
Base Metals : Iron, Cu, and alloys like
Brass. Anodic Metals: Mg, Zn, Al.
E.g.: - Pipe lines, ship hulls Industrial tanks, steel rods are protected by connecting by a wire
to more anodic metal.

Page 5 of 27
 Corrosion Penetration Rate (CPR)
The Corrosion penetration rate is the speed at which any metal or alloy deteriorates in a
specific corrosive environment through chemical or electrochemical reactions. It is also
defined as the amount of weight loss per year in the thickness of metal or alloy due to
corrosion. The Corrosion penetration rate also referred as corrosion rate.
Corrosion penetration rate depends on following factors;
1. Nature of metal.
2. Nature of corrosive environment/medium.
3. Nature corrosion product.
4. Speed at which corrosion spreads in the inner portion of
metal. The Corrosion penetration rate is calculated using the following
formula;
𝐤 𝐱
𝐖
𝐂𝐏𝐑 =
Where, 𝐃(𝛒) 𝐱 𝐀 𝐱 𝐓

W is weight loss after exposure time.

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D or 𝛒 is the density of metal or alloy.

T is exposure time in corrosive medium.

A is surface area of exposed specimen.

K is constant.
The CPR is conveniently expressed in terms of either mils (0.001 inch) per year (mpy) or
millimeters per year (mmpy). K=534 to give CPR in mpy when surface area of test specimen
is in inch2 and K=87.6 for CPR in mmpy when surface area of test specimen is in cm2
Where, 1 mil =0.001 inch
CPR in mpy CPR mmpy
K 534 87.6
W (wt loss) mg mg
3
(D)ρ g/ cm g/ cm3
A inch2 cm2
t hrs Hrs
Numerical Problems on CPR
1. A sheet of carbon steel one meter wide by three meters long has lost 40g to corrosion over the past six
months. Convert that mass loss to a penetration rate of the steel in mm units and mpy units. What would be the
corrosion rate? (Carbon steel density=7.8g/ cm3) To calculate CPR in mmpy
Solution:
Given CPR in mmpy CPR in mpy

K 87.6 534

W (wt loss) 40 g 40 x 1000 mg 40 x 1000 mg

(D)ρ 7.8 g/ cm3 7.8 g/ cm3 7.8 g/ cm3

A 1mx3m=3m2 3x100 x 100 cm2 3 x 1550 inch2

T 6 months 6 x 30 x 24 hrs 6 x 30 x 24 hrs

1 sq mt= 1550 sq inch

𝐂𝐏𝐑 =
𝐤 𝐱𝐖
To calculate CPR in mmpy
𝐃(𝛒) 𝐱 𝐀 𝐱
𝐓

Page 6 of 27
 87.6 X 40 X 1000
7.8
CPR =X 3 X100 X 100 X 6 X 30 X 24

CPR = 3.466 X10-3 mmpy

𝐂𝐏𝐑 =
𝐤 𝐱 𝐖
To calculate CPR in mpy
𝐃(𝛒) 𝐱 𝐀 𝐱 𝐓
534 X 40 X 1000
CPR = 7.8 X 3 X100 X 100 X 6 X 30 X 24
CPR = 0.1363 mpy
2. Calculate the CPR in both mpy and mmpy for a thick steel sheet of area 100 inch2 which experiences a weight
loss of 485g after one year. (Density of steel=7.9g/cm3).
Solution:
Given CPR in mmpy CPR in mpy

K 87.6 534

W (wt loss) 485 g 485 x 1000 mg 485 x 1000 mg

Ρ 7.9 g/ cm3 7.9 g/ cm3 7.9 g/ cm3

A 100 inch2 100 x 6.45cm2 100 inch2

365 x 24 hrs
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T 1 year 365 x 24 hrs

1 inch2= 6.45 cm2, 1 cm2 = 0.155 inch2

𝐂𝐏𝐑 =
𝐤 𝐱 𝐖
To calculate CPR in mmpy
𝐃(𝛒) 𝐱 𝐀 𝐱 𝐓

87.6 X 485 X 1000

CPR =7.9 X 100 X 6.45 X 365 X 24

CPR = 0.9518 mmpy

To calculate CPR in mpy 𝐏𝐑 =

𝐤 𝐱𝐖

𝐃(𝛒) 𝐱 𝐀 𝐱 𝐓
534 X 485 X
1000 =
7.9 X 100 X 365 X 24
CPR CPR = 37.424 mpy
2
3. A thickness of brass sheet of area 400 inch 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/cm 3. Calculate the
CPR in mm/yearmpy.
Solution:
Given CPR in mmpy CPR in mpy

K 87.6 534

W (wt loss) 375 g 375 x 1000 mg 375 x 1000 mg

Ρ 8.73 g/ cm3 8.73 g/ cm3 8.73 g/ cm3

A 400 inch2 400 x 6.45cm2 400 inch2

T 2 year 2 x 365 x 24 hrs 2 x 365 x 24 hrs

1 inch2= 6.45 cm2, 1 cm2 = 0.155 inch2

To calculate CPR in mmpy

𝐂𝐏𝐑 =
𝐤 𝐱 𝐖

𝐃(𝛒) 𝐱 𝐀 𝐱 𝐓

87.6 X 375 X 1000

CPR =8.73 X 400 X 6.45 X 2 X365 X 24

Page 7 of 27
 CPR =0.083mmpy

To calculate CPR in mpy

𝐂𝐏𝐑 =
𝐤 𝐱 𝐖

𝐃(𝛒) 𝐱 𝐀 𝐱 𝐓

534 X 375 X 1000

CPR8.73
= X 400 X 365 X 24X2

CPR = 3.27 mpy

4. 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:
Given
K 534
W (wt loss) 1.2 kg 1.2 x 1000 x 1000mg
Ρ 7.87 g/ cm3 7.87 g/ cm3
A 20 inch2 20 inch2
T ?
CPR mpy 400 400
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𝐂𝐏𝐑 =
𝐤 𝐱 𝐖
To calculate time in years

𝐃(𝛒) 𝐱 𝐀 𝐱 𝐓

k x W
T = D(ρ) X A X
CPR

534 X 1.2 X 1000 X 1000

T= 7.87 X 20 X 400

T= 10177.89 hrs

Converted into years

10177.89
T= 365X 24 = 1.16 yrs

5. A piece of corroded aluminum 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 2.4mmy for this alloy in sea water, estimate the time in years, density of aluminium 2.7 g/
cm3. Solution:
Given
K 87.6
W (wt loss) 350 g 350x 1000mg
Ρ 2.7 g/ cm3 2.7 g/ cm3
A 64 cm2 64 cm2
T ?
CPR mmy 2.4 2.4
To calculate time in years

𝐂𝐏𝐑 =
𝐤 𝐱 𝐖

𝐃(𝛒) 𝐱 𝐀 𝐱 𝐓
k x W
T = D(ρ) X A X
CPR

87.6 X 350 X 1000

T= 2.7 X 64 X 2.4

Page 8 of 27
 T= 73929.39 hrs

Converted into years

T = 73929.39 = 8.44 yrs

365X 24

5. The alloy bronze exposed to different corrosive environment of area 50 cm2, for a period of 6
months. The bronze alloy loss of weight in acidic medium was 200 g, in neutral 120 g and in
basic medium 48 g. Calculate the CPR in mpy. (Density of bronze =8.73g/ cm3)
Solution: In acidic medium

Given CPR in mpy

K 534
W (wt loss) 200 g 200 x 1000 mg
Ρ 8.73 g/ cm3 8.73 g/ cm3
A 50 cm2 50 x 0.155 inch2
T 6 months 6 x 30 x 24 hrs

𝐂𝐏𝐑 =
𝐤 𝐱 𝐖
1 cm2 = 0.155 inch2

𝐃(𝛒) 𝐱 𝐀 𝐱 𝐓
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534 X 200 X 1000

CPR = 8.73 X 50 X 0.155 X 6 X 30X 24

CPR = 365.40 mpy

In neutral medium
Given CPR in mpy
K 534
W (wt loss) 120 g 120 x 1000 mg
Ρ 8.73 g/ cm3 8.73 g/ cm3
A 50 cm2 50 x 0.155 inch2
T 6 months 6 x 30 x 24 hrs

534 X 120 X 1000

CPR = 8.73 X 50 X 0.155 X 6 X
CPR = 219.24 mpy
In basic medium 30X 24

Given CPR in mpy

K 534
W (wt loss) 48 g 48 x 1000 mg
Ρ 8.73 g/ cm3 8.73 g/ cm3
A 50 cm2 50 x 0.155 inch2
T 6 months 6 x 30 x 24 hrs

534 X 48 X 1000
CPR8.73
= X 50 X 0.155 X 6 X 30X 24

CPR = 87.70 mpy

7. A zinc rods is dipped in a NaCl solution of area 20 inch 2 each at different temperature. The metal zinc undergone
corroded of 50g at 338 K, 30g at 323K, 10 g at 300 K over a period of one month. Determine the CPR in terms
of mmpy. (Density of Zinc = 7.12 g/ cm3)
Solution:
To calculate CPR in mmpy at 338K

Page 9 of 27
 Given CPR in mmpy
K 87.6
W (wt loss) 50 g 50 x 1000 mg
Ρ 7.12 g/ cm3 7.12 g/ cm3
2
A 20 inch 20 x 6.45cm2
T 1 month 30 x 24 hrs
2 2
1 inch = 6.45 cm

𝐂𝐏𝐑 =
𝐤 𝐱 𝐖

𝐃(𝛒) 𝐱 𝐀 𝐱 𝐓

87.6 X 50 X 1000
CPR7.12
= X 20 X 6.45 X 30 X 24

CPR =6.60mmpy

At 323K
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Given CPR in mmpy

K 87.6
W (wt loss) 30 g 30 x 1000 mg
Ρ 7.12 g/ cm3 7.12 g/ cm3
2
A 20 inch 20 x 6.45cm2
T 1 month 30 x 24 hrs
2 2
1 inch = 6.45 cm

87.6 X 30 X 1000
CPR =7.12 X 20 X 6.45 X 30 X 24

CPR =1.32mmpy

At 300K

Given CPR in mmpy

K 87.6

W (wt loss) 10 g 10 x 1000 mg

Ρ 7.12 g/ cm3 7.12 g/ cm3

A 20 inch2 20 x 6.45cm2

T 1 month 30 x 24 hrs

1 inch2= 6.45 cm2

87.6 X 10 X 1000
CPR =7.12 X 20 X 6.45 X 30 X 24

CPR =3.97mmpy
Page 10 of 27
 8. A copper plates of length of 2 cm and width of 5 cm were kept in a salt solution of pH - 3, loss of metal was
1 g, at pH – 8 of the solution was 0.8 g and at pH – 12 of the solution was 0.2 g in a one year of period.
Estimate the CPR of Copper in terms of mmpy. (Density of the copper – 8.96 g/cm3)

Solution:
To calculate CPR in mmpy At

pH – 3 of the salt solution

Given CPR in mmpy
K 87.6
W (wt loss) 1g 1 x 1000 mg
3
Ρ 8.96 g/ cm 8.96 g/ cm3
A 2 cm x 5 cm 10 cm2
T 1 year 365 x 24 hrs

𝐂𝐏𝐑 =
𝐤 𝐱 𝐖

𝐃(𝛒) 𝐱 𝐀 𝐱 𝐓
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87.6 X 1 X 1000
CPR8.96
= X 10 X 365 X 24

CPR =0.112mmpy

At pH – 8 of the salt solution

Given CPR in mmpy
K 87.6
W (wt loss) 0.8g 0.8 x 1000 mg
Ρ 8.96 g/ cm3 8.96 g/ cm3
A 2 cm x 5 cm 10 cm2
T 1 year 365 x 24 hrs

87.6 X 0.8 X
1000 =
8.96 X 10 365 24
CPR CPR =0.09 mmpy
X X

At pH – 12 of the salt solution

Given CPR in mmpy
K 87.6
W (wt loss) 0.2g 0.2 x 1000 mg
Ρ 8.96 g/ cm3 8.96 g/ cm3
A 2 cm x 5 cm 10 cm2
T 1 year 365 x 24 hrs

87.6 X 0.2 X
1000 =
8.96 X 10 365 24
CPR CPR =0.022 mmpy
X X

9. Estimate the corrosion period (in years) of metal tin bar exposed to environment of summer, the
surface area of 20 inch2, 0.8mpy of CPR with a loss of 730 mg tin. The density of tin is 7.31g/cc.

Page 11 of 27
 𝐂𝐏𝐑 =
𝐤 𝐱 𝐖
Solution: To calculate time in years
𝐃(𝛒) 𝐱 𝐀 𝐱 𝐓
k x W
T = D(ρ) X A X
CPR
Given
K 534
W (wt loss) 730 mg 730 mg
Ρ 7.31 g/ cm3 7.31 g/ cm3
A 20 inch2 20 inch2
T ?
CPR mpy 0.8 0.8

534 X730
T = 7.31 X 20 X 0.8

T = 3335.93 hrs

Convert into years

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3332.93
T = 365 X24 = 0.38 yrs

10. A thickness of alloy sheet of area 100 inch 2 is exposed to air near the ocean. After 1 year period it was found
to experience a weight loss of 35gdue to corrosion. If the density of alloy is 8.4 g/cm3. Calculate the CPR in
mmy and mpy.
Solution:

Given CPR in mmpy CPR in mpy

K 87.6 534
W (wt loss) 35 g 35 x 1000 mg 35 x 1000 mg
Ρ 8.4 g/ cm3 8.4 g/ cm3 8.4 g/ cm3
A 100 inch2 100 x 6.45cm2 100 inch2
T 1 year 365 x 24 hrs 365 x 24 hrs
1 inch2= 6.45 cm2
1 cm2 = 0.155 inch2
To calculate CPR in mmpy

𝐂𝐏𝐑 =
𝐤 𝐱 𝐖

𝐃(𝛒) 𝐱 𝐀 𝐱 𝐓

87.6 X 35 X 1000
CPR8.4
=X 100 X 6.45 X 365 X 24

CPR = 0.064 mmpy

To calculate CPR in mpy

𝐂𝐏𝐑 =
𝐤 𝐱 𝐖

𝐃(𝛒) 𝐱 𝐀 𝐱 𝐓

534 X 35 X 1000
CPR8.4
= X 100 X 365 X 24

CPR = 2.54 mpy

Page 12 of 27
 Electrode System
An electrode is a solid conductor that carries electric current into non-metallic solids, or
liquids, or gases, or plasmas, or vacuum. In an electrochemical cell, reduction and oxidation
reactions take place at the electrodes.
Examples of typical materials used for electrodes are amorphous carbon, metals like Zinc,
Copper, gold, and platinum.

Types of electrodes Electrodes.

1. Metal-metal Ion electrode: In this type of electrode metal will be dipped in its own
ionic solution. Ex: Zn rod dipped in ZnSO₄ (zinc sulphate) solution, Cu rod dipped in
CuSO4 (copper sulphate) solution
2. Metal-metal insoluble salt electrode: This type of electrode a metal electrode will be
in contact with its insoluble metal salt dipped in a solution containing an anion of the
salt. Ex: Calomel and Ag-AgCl electrodes
3. Gas electrode: An inert metal electrode like Platinum (Pt) will be in contact with gas
molecules and which is dipped in ionic solution of the same gas molecules.
Ex: SHE - Pt/H2 / [H+] 1M HCl.
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4. Amalgam electrode: It is similar to metal-metal Ion electrode, but here metal

amalgam (Metal + Mercury) is in contact with ionic solution metal.
Ex: Lead-Amalgam electrode Pb-Hg/Pb+2, Zinc-Amalgam electrode Zn-Hg/Zn2+.
5. Redox electrode (Oxidation-Reduction electrode): Redox Electrode measures the
oxidation or reduction potential of the oxidized and reduced forms of the same
substance in a solution. The potential of the redox electrode depends on oxidized and
reduced forms in the solution. Ex: Platinum electrode Pt- Fe²⁺/Fe³⁺.
6. Ion-selective electrodes (Membrane Electrode): These electrodes are selectively
sensitive to a particular kind of ions in a mixture of ionic solution and develop
potential across membrane ignoring other ions. Ex: Glass electrode.

Reference Electrodes
Reference electrodes are electrodes which are used to determine single electrode
potential of an unknown electrode.
There are two types of reference electrodes i.e.
1. Primary Reference Electrode
E.g. Standard Hydrogen Electrode (SHE) or Gas Electrode.
2. Secondary Reference Electrodes.
E.g. Calomel Electrode (Hg2 Cl2 / Hg), Ag – AgCl Electrode
Limitations of Primary Reference Electrode – SHE
1. Difficult to setup.
2. Electrodes become inactive in presence of impurities in H2 gas.
3. Cell potential is not reproducible.
4. Difficult to maintain constant pressure(1atm) of the gas
Hence to measure the electrode potential, Secondary reference electrodes such as Calomel
Electrode & Ag/AgCl Electrode are used.
Advantages of Secondary Reference Electrodes.
1) Secondary reference electrodes are simple to construct.
2) Cell potential is reproducible & stable.
3) Cell potential does not vary with temperature. Hence it is used as secondary reference
electrode.
Page 13 of 27
 Calomel electrode – (Hg2 Cl2 / Hg Electrode)
Calomel electrode is a metal – metal insoluble salt electrode. It is constructed as
follows. Calomel electrode consists of a glass tube. A small quantity of mercury is placed at
the bottom of the tube on which a calomel paste [mixture of Hg 2Cl2 + Hg] is placed. The
remaining part is filled with saturated or standard solution of KCl. The side tube serves as salt
bridge. A platinum wire fused in glass tube is dipped in Mercury serves as an electrical
contact.

The half-cell is represented as,

KCl(sat) / Hg2 Cl2(S) ; Hg /
Pt Wire
Pt

The half-cell reaction depends on whether

it is connected to anode or cathode. Salt Bridge
KCl (Sat)

As Anode
2Hg Hg22+(aqs) + 2e
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Hg22+(aqs) + 2 Cl – Hg2 Cl2

2 Hg + 2 Cl– Hg2 Cl2 + 2e

As Cathode
Hg2 Cl2 Hg22+(aqs) + 2 Cl –
Hg22+(aqs) + 2e 2 Hg.
Hg2 Cl2 + 2e 2 Hg + 2 Cl – Calomel Paste
(Hg +Hg2 Cl2)
The potential of the calomel electrode depends on the
concentration of KCl solution used.
Hg
For 0.1 M KCl – E = + 0.334V.
1 M KCl – E = + 0.281V.
Sat KCl – E = + 0.241V.

Ion Selective Electrodes (ISE)

“Ion selective electrodes are membrane electrodes, which are selectively sensitive to particular
kind of Ions in a mixture of ionic solution & develop potential across membrane”.

Principle: - Ion selective electrodes have the ability to respond to certain specific ions in a
mixture of ionic solution while ignoring other ions & develop a potential across the
membrane.

The cell is illustrated as, Membrane

External Solution to be Internal Solution Internal

Ref Electrode Analysed [Mn+] = C2 Ref Electrode.
(1) [Mn+] = (2)
C1= ?

The membrane potential (boundary Potential) Eb is difference between two potentials E1&
E2. Potentials E1& E2 arise due to the solution to be analyzed (C1) on outer side of the
membrane and internal standard solution (C2) on inner side of the membrane respectively.
Page 14 of 27
Therefore, E b = E1 – E 2

Page 15 of 27
 Eb = 2.303 RT log [C1] – 2.303 RT log[C2]
nF nF

Eb = 2.303 RT log [C1] – Constant [C]2= Concentration of internal standard

solution
nF
OR

Eb = Constant + 2.303 RT log [C1] C1 = H + ; n =

1 nF
Eb = Constant + 0. 0591 log [H +] pH = – log [H +]

Pt Wire
Eb = L’ – 0. 0591 pH L’ = Constant.

Glass Electrode
Construction: - Glass electrode consists of a thin walled (0.001mm)
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glass bulb, which is made up of special glass of low M.P. & high 0.1M HCl
electrical conductivity. The composition of the glass is 22% Na 2O,
6% CaO & 72% [Link] glass bulb contains 0.1M HCl in which
Ag/AgCl electrode is dipped acts as internal Ref electrode. This
glass membrane can sense H+ ions up to a pH of 9, above pH 9 the
glass
becomes sensitive to Na+ instead of H+ ions. This is known as
“Alkaline Error”. Hence special glass membranes are used to
measure pH above 9.

Electrode is represented as,

Ag, AgCl(s) / 0.1 M HCl / Glass

The glass electrode reaction across the membrane Ag /AgCl

Internal Ref.
H+ + Na+ Gl – Na+ + H+ Gl – Electrode

Solution Membrane Solution Membrane Glass

Membrane
Reaction indicates ion exchange process between solution
& membrane. When glass electrode is dipped into any
solution containing H+ ions & if concentrations of Solution
inside & outside the glass membrane are different, then a
potential develops across the glass membrane. This is due
to the ion exchange process between Glass membrane
[Na+] & Solution [H+].
Potential of glass electrode EG is given by,
EG = Eb + ERef + E Asym
Eb = Boundary potential.
Eref = Internal reference electrode potential (Ag/AgCl).
Easym = Asymmetric potential when C1 = C2
Page 16 of 27
 Dept of Chemistry
Applied Chemistry for Computer Science & Engineering stream

MODULE 3
EG = Eb + EAg/AgCl + E

But, Eb= L’ – 0. 0591 pH

Therefore,
EG = L’ – 0. 0591 pH + EAg/AgCl + E Asym

EG = E0G – 0. 0591 pH Where E0G Represents 3 Constants

L’, EAg/AgCl , E Asym

NOTE: Membrane electrode is always considered as cathode.

Advantages [Merits]
1. It can be used in the presence of strong oxidizing & reducing agents as the membrane is
unaffected by the presence of strong oxidizing & reducing agents.
2. Very simple to operate.
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3. The equilibrium between two solutions (Inner & Outer solutions) is reached quickly.
4. Provides accurate results.
Disadvantages
1. Glass electrode cannot be used in presence of Fluoride Ions.
2. Difficult to construct.
3. The bulb is too fragile.
4. Cannot be used above pH 9, as it develops alkaline error.

Determination of pH using Glass Electrode.

To determine the pH of a given solution, the glass electrode is dipped into the given
solution & is combined with a calomel electrode through a salt bridge. The e.m.f of the cell is
measured using electronic voltmeter. The cell assembly is represented as.
C1 C2 Electronic Voltmeter

Calomel electrode / Test Solution / Glass / 0.1M HCl /AgCl,

Ag
PH=?

The cell potential is

E cell = ER – EL
Glass
= EG – E cal (1) Electrode
Calomel
When glass electrode containing an acid [H+] = is immersed
Electrode
C2
in a (given) solution [H+] = C1 a potential arises across Soln. to be
the membrane given by the equation analysed = C 1
Internal Soln
(0.1M)=C2
EG = Eb + ERef + E Asym

Eb = Boundary potential.
Eref = Internal reference electrode potential (Ag/AgCl).
Easym = Asymmetric potential when C1 = C2
Even Semester 2022
-23
 Dept of Chemistry
Applied Chemistry for Computer Science & Engineering stream

MODULE 3
EG = Eb + EAg/AgCl + E
But Eb= L’ – 0. 0591 pH
Therefore,

EG = L’ – 0. 0591 pH + EAg/AgCl + E Asym

Where E0G Represents 3 Constants

EG = E0G – 0. 0591 pH ……. (2) L’, EAg/AgCl , E Asym

Substituting Eqn. (2) in (1)

Ecell = E0G – 0. 0591 pH – Ecal

0. 0591 pH = E0G – Ecal – Ecell

pH = E0G – Ecal – EcellWhere Ecal & EoG are constants.

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0. 0591
By substituting e.m.f of the cell in above equation, pH of unknown (given) solution is
calculated.

Concentration Cell
“A concentration cell is an Electrochemical cell in which two identical electrodes are
immersed in same ionic solution but of different ionic concentrations”. As a result the
potential difference arises due to transfer of a substance from the solution of higher
concentration to the solution of lower concentration. An example of concentration cell is, two
identical copper electrodes dipped in 1M copper nitrate and 2M copper nitrate.

The

concentration cell is represented as Cu(s) / Cu2+(aqs) (1M) // Cu2+(aqs) (2M) / Cu(s)

Even Semester 2022

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 Dept of Chemistry
Applied Chemistry for Computer Science & Engineering stream

MODULE 3
In concentration cell net cell reaction is simply change in concentrations as a result of which
current flows.

E.m.f of the cell is given as,

E cell = E right – E left
According to Nernst equation
E cell = [Eo + 0.0591 log[M2]] – [Eo + 0.0591 log [M1]]
n n
E cell = 0.0591 log [M2]
n [M1]

Where M2>M1 [Molar Concentration of metal ions]

Conclusions
1. Value of e.m.f i.e. Ecell is +Ve as long as there is a difference in concentrations.
2. The concentration of anode compartment increases, while it decreases in cathode
compartment.
3. The cell can produce current till the concentration of electrolyte in the two half-cells
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become equal. If M2 = M1, [M2/M1] = 1 , log(1) = 0 :. E = 0

4. Higher the ratio M2 / M 1 higher is the value of cell potential. If ratio [M2/M1] is increased
from 0.001 to 0.01 (10times) the voltage doubles &if increased from 0.001 to 0.1(100
times) the voltage increases three folds.
Numerical Problems on Concentration Cells
1. A concentration cell was constructed by immersing two silver electrodes in 0.01M &
10M AgNO3 solution. Calculate e.m.f of the cell.

Solution:
Concentration of AgNO3 at anode [M1] = 0.01M
Concentration of AgNO3 at Cathode [M2] = 10 M
Number of moles of electrons (n) =1

Ecell= 0.0591 log[M2]

n [M1]

Ecell= 0.0591 log[10M]

1 [0.01M]

Ecell= 0.1773V

2. Calculate e.m.f. of the cell at 298K, Cd(s)/Cd2+(aqs)(0.01M)//Cd2+

(aqs)(0.1M)/Cd(s) Solution:
Concentration of Cd2+ ions at anode [M1] = 0.01M
Concentration of Cd2+ ions at Cathode [M2] = 0.1
M Number of moles of electrons (n) =2

Ecell= 0.0591 log[M2]

n [M1]

Even Semester 2022

-23
 Dept of Chemistry
Applied Chemistry for Computer Science & Engineering stream

MODULE 3
Ecell= 0.0591 log[0.1M]
2 [0.01M]

Ecell= 0.02955V

3. Calculate the e.m.f of the cell, Cu(s) / Cu2+(aqs) (0.072M) // Cu2+(aqs) (0.32M) /
Cu(s).Comment on the spontaneity of the cell reaction.

Solution:
Concentration of Cu2+ ions at anode [M1] = 0.072M
Concentration of Cu2+ ions at Cathode [M2] =
0.32M Number of moles of electrons (n) =2

Ecell= 0.0591 log[M2]

n [M1]

Ecell= 0.0591 log[0.32 M]

2 [0.072 M]
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Ecell= 0.01914V

The e.m.f. of the cell is positive i.e. +0.1914 Volts hence the cell reactions are spontaneous.

4. Calculate the e.m.f of the following concentration cell at

298K. Ag(s)/Ag+(aqs)(0.01M)//Ag+(aqs)(0.5M)/Ag(s)

Solution:
Concentration of Ag+ ions at anode [M1] = 0.01M
Concentration of Ag+ions at Cathode [M2] = 0.5M
Number of moles of electrons (n) =1
Ecell= 0.0591 log[M2]
n [M1]

Ecell= 0.0591 log[0.5 M]

1 [0.01 M]

Ecell =0.1004V

5. Calculate the e.m.f the following concentration cell at 250 C

Zn(s)/Zn2+(aqs)(0.024M)//Zn2+(aqs)(0.048M)/Zn(s)

Solution:
Concentration of Zn2+ ions at anode [M1] = 0.024M
Concentration of Zn2+ ions at Cathode [M2] =
0.048M Number of moles of electrons (n) =2

Ecell= 0.0591 log[M2]

n [M1]

Even Semester 2022

-23
 Dept of Chemistry
Applied Chemistry for Computer Science & Engineering stream

MODULE 3
Ecell= 0.0591 log[0.048 M]
2 [0.024M]
Ecell= 0.008895V

6. The following concentration cell at 25 0 C consisting of Zinc electrode immersed in a

solution of zinc ions of 1.5 molar and 0.01 molar concentrations. Write the cell
scheme, cell reactions & calculate e.m.f of the cell.
Solution:
Concentration of Zn2+ ions at anode [M1] = 0.01M
Concentration of Zn2+ ions at Cathode [M2] = 1.5 M
Number of moles of electrons (n) =2

Cell scheme: →
Zn(s) / Zn (aqs) (0.01M) // Zn2+ (aqs) (1.5M) /Zn(s)
2+

Cell Reactions:
At Anode Zn(s) (aqs) (0.01M) + 2e -Oxidation
Zn2+
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At Cathode Zn2+ (aqs) (1.5M) + 2e Zn (s) -Reduction

Zn2+ (1.5M)
2+
Zn (0.01M) - Net cell reaction. aqs)
aqs)

Ecell= 0.0591 log[M2]

n [M1]

Ecell= 0.0591 log[1.5 M]

2 [0.01 M]

Ecell = 0.0643V

7. Calculate the e.m.f. of the concentration cell Ag(s) / AgNO3(aqs) (0.018M) // AgNO3(aqs)
(1.20M) / Ag(s). If water is added to the more dilute solution, what happens to the
e.m.f of the cell? Explain your answer.
Solution:
Concentration of Ag+ ions at anode [M1] = 0.018M
Concentration of Ag+ ions at Cathode [M2] = 1.2 M
Number of moles of electrons (n) =1

Ecell= 0.0591 log[M2]

n [M1]

Ecell= 0.0591 log[1.2 M]

1 [0.018 M]

Ecell= 0.1077V

If water is added to the more dilute solution [M1], at anode the ratio of [M2] increases
hence the e.m.f of the cell also increases. [M1]

Even Semester 2022

-23
Dept of Chemistry
Applied Chemistry for Computer Science & Engineering stream

MODULE 3
8. Calculate the e.m.f the following concentration cell at 298 K consisting of Zinc
electrode immersed in a solution of Zinc ions of 2.5 molar and 0.05 molar
concentrations. Write cell notation and electrode reactions.
Solution:
Concentration of Zn2+ ions at anode [M1] = 0.05M
Concentration of Zn2+ ions at Cathode [M2] = 2.5 M
Number of moles of electrons (n) =2

Cell scheme: →
Zn(s) / Zn (aqs) (0.05M) // Zn2+ (aqs) (2.5M) /Zn(s)
2+

Cell Reactions:
At Anode Zn(s) (aqs) (0.05M) + 2e -Oxidation
Zn2+
At Cathode Zn2+ (aqs) (2.5M) +2e Zn (s) -Reduction
Zn2+ (2.5M)
2+
Zn (0.05M) - Net cell reaction. aqs)
aqs)

Ecell= 0.0591 log[M2]

n [M1]

Ecel l= 0.0591 log[2.5 M]

2 [0.05 M]
Ecell = 0.0502V

9. The cell potential of concentration cell Ag(s)/AgNO3(aqs)(0.002)//AgNO3(aqs)(XM)/Ag(s)

is 0.0751 V at 25 °C. Write the cell reactions and calculate the value of X.
Solution:
Concentration of Ag+ ions at anode [M1] = 0.002
Concentration of Ag+ ions at Cathode [M2] = X M
Cell potential of Ag concentration cell, Ecell = 0.0751 V
Number of moles of electrons (n) =1
At Anode Ag(s) Ag+(aqs) (0.002M) + 1e - Oxidation
At cathode Ag+(aqs) (XM) +1e Ag(s) -
Reduction
Ag+(aqs) (XM) Ag+(aqs) (0.002M) - Net cell reaction

Ecell= 0.0591 log[M2]

log[𝑀2] = Ecell× 𝑛
n [M1]
[𝑀1] 0.0591
1
[𝑀2] = 0.0751 ×
log [0.002 0.0591
𝑀]
= 1.270
[𝑀2]
log[0.002
𝑀]
[𝑀2]
[0.002
= Antilog (1.270)
𝑀]
[𝑀2] = 18.652
[0.002
𝑀]

Even Semester 2022

-23
 Dept of Chemistry
Applied Chemistry for Computer Science & Engineering stream

MODULE 3
[𝑀2] = 18.652 x 0.002
[𝑴𝟐] = 0.0373 M

Concentration of Ag+ ions at Cathode [M2] = 0.0373 M

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Even Semester 2022

-23
 Dept of Chemistry
Applied Chemistry for Computer Science & Engineering stream

MODULE 3
10. The following concentration cell at 25 °C consists of zinc electrode immersed in a
solution of zinc ions of 1.5 molar at cathode and EMF of the cell is 0.0643 V. Write the
cell scheme, cell reactions and calculate concentration of zinc ions at anode.
Solution:
Concentration of Zn2+ ions at anode [M1] = XM
Concentration of Zn2+ ions at Cathode [M2] = 1.5 M
Cell potential of Ag concentration cell, Ecell = 0.0643V
Number of moles of electrons (n) = 2

Cell scheme Zn(s)/Zn2+(aqs)(XM)//Zn2+(aqs)(1.5M)/Zn(s)

Cell reactions
At Anode (aqs) (XM) + 2e - Oxidation
Zn2+(aqs) (1.5M) +2e Zn(s) - Reduction
Zn(s)Zn2+ At cathode (aqs)
Zn2+(aqs (1.5M) Zn2+ (XM) - Net cell reaction
)

Ecell= 0.0591 log[M2]

log[𝑀2] = Ecell × 𝑛
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n [M1]
[𝑀1] 0.0591

log[1.5] = 0.0643× 2
[𝑀 0.0591
1]

[1.5]
= 2.1759
log [𝑀
1]
[1.5]
[𝑀1]
= Antilog (2.1759)

[1.5]
[𝑀1]
= 149.959

[𝑀1] = 1.5
149.959

[𝑴𝟏] = 0.0100 M

Concentration of Zn2+ions at anode [M1] = 0.0100 M

Even Semester 2022

-23
 Dept of Chemistry
Applied Chemistry for Computer Science & Engineering stream

MODULE 3
Estimation of FAS Potentiometrically using standard K 2Cr2O7 solution
using potentiometric sensor.
Definition: Potentiometric measures the oxidation or reduction potential of the
oxidized and reduced species of the same substance in a solution. The potential of the
redox electrode depends on oxidized and reduced forms in the solution.

Theory: Redox titrations can be carried out Potentiometrically using platinum-

calomel electrode combination similar to acid-base neutralizations. For the reaction:
Reduced form → oxidized form + n electrons
𝟎. 𝟎𝟓𝟗𝟏 [𝐨𝐱𝐢𝐝𝐢𝐳𝐞𝐝𝐟𝐨𝐫𝐦]
The potential is given by Nernst equation:
𝐄 = 𝐄° + 𝐥𝐨𝐠
𝐧 [𝐫𝐞𝐝𝐮𝐜𝐞𝐝𝐟𝐨𝐫𝐦]
Where E0 is the standard potential of the system. The potential of the system is thus
controlled by the ratio of the concentration of the oxidized to that of the reduced species
present. As the reaction proceeds, the ratio of concentration of the oxidized to that of the
reduced species varies and hence the potential change more rapidly in the vicinity of the end
point of the titration. This may be followed Potentiometrically and a plot of change in
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potential against volume (titration curve) is characterized by a sudden change of potential at

the Equivalence point. The sudden change in the potential at the Equivalence point is
explained as follows:
The reaction that takes place in the determination of Fe2 +is:
Fe2 + Fe3 ++ e– - Oxidation
Cr2O7 + 14 H +6 e–
2– +
2Cr3++ 7H2O - Reduction.

Prior to addition of K2 Cr2 O7 to the acidified FAS in beaker the potential will be low due to
Fe2 + ions. On addition of K2 Cr2 O7 oxidation of Fe2 + to Fe3 + takes place and potential
increases progressively.
E Fe3+ / Fe2 + = E o Fe3+ / Fe2 + + 0.0591 log [Oxidized Form]
n [Reduced Form]

E Fe3+ / Fe2 + = E o Fe3+ / Fe2 + + 0.0591 log [Fe3+]

n [Fe2+]

E Fe3+ / Fe2 + = - 0.44V + + 0.0591 log [Fe3+]

n [Fe2+].........................(1)

At equivalence point all Fe2 + will completely oxidize to Fe 3 + and potential increases rapidly.
And hence e.m.f of the cell also increases.

The e.m.f of the cell is given by the equation:

Ecell = ECathode – EAnode.
Ecell = E Fe3+ / Fe2 + – ESCE
Ecell = E Fe3+ / Fe2 + – 0.242V..........................(2)

Ecell = E Fe3+ / Fe2 + = - 0.44V + + 0.0591 log [Fe3+] – 0.242V

n [Fe2+]

Beyond the Equivalence point the potential is because of Cr2O72–/Cr3+.

Even Semester 2022

-23
 Dept of Chemistry
Applied Chemistry for Computer Science & Engineering stream

MODULE 3
Thus, an abrupt increase in the potential of the solution in the vicinity of the equivalence
point is observed. This marks the equivalence point. In the experiment, the potential of the
cell is determined with reference to Saturated Calomel Electrode.

Procedure
Transfer 25.0 cm3of ferrous ammonium sulphate solution into a clean 250 cm3 beaker
with the aid of pipette. Add two test tubes of dilute Sulphuric acid. Immerse the Calomel-
Platinum electrode assembly into the solution in the beaker and connect the electrode
assembly to potentiometer. Measure the potential (E). Fill the burette with potassium
dichromate solution. Add 0.5cm3 of K2Cr2O7 solution to the beaker at a time. Stir the solution
carefully and measure the potential after 30 seconds. Continue the addition of K 2Cr2O7 till
there is a sudden rise in potential (At this stage wait for 5 minutes). Continue the titration in
the same way till
10 ml. Determine the end point by differential method ( that is by plotting a graph of ∆𝐸 against
∆𝑉
volume of K2Cr2O7 as shown in the figure). Calculate the normality and amount of FAS in the
given solution.

Observations & Calculations:

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Volume of E ∆E ∆V ∆E/∆V
K2Cr2O7 (mV) (mV) (cm3) (mV/
(cm3) cm3)
0.0
0.5
1.0
1.5
Up to 10.0

Equivalence Point = VK2Cr2O7 = ………cm3

𝐍𝐅𝐀𝐒𝐕𝐅𝐀𝐒 = (𝐍𝐊𝟐𝐂𝐫𝟐𝐎𝟕)(𝐕𝐊𝟐𝐂𝐫𝟐𝐎𝟕)

(𝐍𝐊𝟐𝐂𝐫𝟐𝐎𝟕)(𝐕𝐊𝟐𝐂𝐫𝟐𝐎𝟕)
𝐍𝐅𝐀𝐒 = 𝐕𝐅𝐀𝐒

Number of grams of FAS in 1000cm3 = 𝐍𝐅𝐀 𝐄𝐪𝐮𝐢𝐯𝐚𝐥𝐞𝐧𝐭 𝐦𝐚𝐬𝐬 𝐨𝐟 𝐅𝐀𝐒

Note: Equivalent mass of FAS = 392.13

Result: (a) 𝐍𝐅𝐀𝐒 = …………….

Amount of FAS in 1000 cm3 of the solution = …g

Even Semester 2022

-23
 Dept of Chemistry
Applied Chemistry for Computer Science & Engineering stream

MODULE 3
Conductometric Estimation of Weak Acid
Definition: The conductometric is one which detect change in the ionic concentration in
an analyte, which leads to a change in electrical conductivity and measure of the
conductance.
Theory: Measurement of conductance can be employed to determine the end point
in acid-base titrations. In conductometric titrations, there is a sudden change in the
conductance of the solution at the equivalence point. The principle underlying
conductometric titration is the substitution of ions of one mobility by ions of another
mobility. Therefore, the conductance of a solution depends on the number and mobility of
ions. The equivalence point is determined graphically by plotting conductance (ordinate)
against the titre values (abscissa).
Conductometric titration may be applied for the determination of acids present in a mixture.
In the titration of a mixture of weak acid (CH 3COOH) and a strong acid (HCl) with a strong
base (NaOH), the conductance decreases upon adding NaOH to the acid mixture owing to the
substitution of the highly mobile H + ions (mobility = 350 mho per meter) by the less mobile
Na+ ions (mobility = 50 mho per meter). This trend continues till all the H + ions of HCl are
replaced (that is, strong acid is completely neutralized). Continued addition of NaOH rises the
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conductance moderately, as the weak acid (CH3COOH) is converted into its salt
(CH3COONa). Further addition of NaOH rises the conductance steeply due to the presence of
free OH– ions (mobility = 198 mho per metre). The titration curves in the graph given depict
the location of the equivalence points.

Initially the conductance is low due to the partial ionization of acetic acid. On the addition of
base, there is decrease in conductance not only due to the replacement of H+ by Na+ but also
suppresses the dissociation of acetic acid due to common ion acetate. But very soon, the
conductance increases on adding NaOH as NaOH neutralizes the un-dissociated CH3COOH
to CH3COONa which is the strong electrolyte. This increase in conductance continues raise
up to the equivalence point. The graph near the equivalence point is curved due the
hydrolysis of salt CH3COONa. Beyond the equivalence point, conductance increases more
rapidly
with the addition of NaOH due to the highly conducting OH− ions.

CH3COOH + NaOH CH3COONa + H2O

Procedure:
Fill a 10 cm3micro burette with the standard (1N) NaOH solution. Pipette out 50 cm 3
of the Weak Acid into a clean 100 cm3 beaker. Immerse the conductivity cell into the weak
acid. Connect the conductivity cell to the conductivity bridge; adjust the cell constant and
measure the conductance (when the volume of NaOH is zero). Now add NaOH solution from
the burette in increments of 0.5 cm3. After each addition of NaOH, mix the solution well and
record the conductance of the solution. As the titration proceeds, the conductance first
gradually decreases, then rises gradually and finally rises sharply.
Plot a graph of conductance (Y - axis) against volume of NaOH (X - axis). The volume
corresponding to the point of intersection of the curve gives neutralization point for
CH3COOH. Calculate the normality and amount of CH3COOH in one 1000cm3 of weak acid.

Even Semester 2022

-23
 Dept of Chemistry
Applied Chemistry for Computer Science & Engineering stream

MODULE 3
Observations and Calculations:
Volume of NaOH Conductivity
(cm3) (ohm1cm1)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5

(𝑵𝑪𝑯𝟑𝑪𝑶𝑶𝑯) (𝑽𝑪𝑯𝟑𝑪𝑶𝑶𝑯) = (𝑵𝑵𝒂𝑶𝑯 ) (𝑽𝑵𝒂𝑶𝑯)

(𝑵𝑵𝒂𝑶𝑯)
𝑵𝑪𝑯𝟑𝑪𝑶𝑶𝑯 =
(𝑽𝑵𝒂𝑶𝑯)
𝑽𝑪𝑯𝟑𝑪𝑶
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𝑶𝑯

Amount of CH3COOH present in 1 dm3 of the acid mixture = NCH3COOH x Equivalent mass of CH3COOH.

Equivalent mass of CH3COOH = 60.05

Result: Normality of CH3COOH = …………….

Amount of CH3COOH /dm3 = ……………

MODULE 3: Question Bank & Scheme of Answers

1. Define corrosion. Explain the electrochemical theory of corrosion taking Iron as an
example.
Answer: Definition for corrosion, Electrochemical Theory- 3 points, Diagram, Anode
oxidation, cathodic reduction 3 type, corrosion current, corrosion product,
2. What are the types of corrosion? Explain differential metal
corrosion. Answer: Differential metal corrosion. Differential aeration
corrosion..
Diagram, Anodic and Cathodic reactions for differential metal corrosion with explanation.
3. Write a note on waterline corrosion and pitting corrosion.
Answer: Explain deferential aeration corrosion, Diagrams of waterline and pitting
corrosion with explanation. Anodic and cathodic reactions.
4. Give reasons, nuts and bolts are made up of same metal.
Answer: Explain differential metal corrosion with diagram.
5. What is Anodizing? Explain Anodizing of aluminium.
Answer: Anodizing : Explain what is anodizing, anodizing process with neat diagram
and applications.
6. What is Galvanizing? Explain Galvanizing process.
Answer: Definition of Galvanizing: Explain anodic metal coating, Diagram, Galvanizing
process.
Even Semester 2022
-23
Dept of Chemistry
Applied Chemistry for Computer Science & Engineering stream

MODULE 3
7. What is Cathodic Protection? Explain sacrificial anode method.
Answer: Explain cathodic protection, diagram and explanation of sacrificial anode method.

Even Semester 2022

-23
 Dept of Chemistry
Applied Chemistry for Computer Science & Engineering stream

MODULE 3
8. What are types of single electrodes? Give brief explanation of
each. Answer: Briefly explain 6 types of single electrodes.
9. What are reference electrodes? Explain the construction and working of a calomel
electrode and mention
Answer: Definition of Reference electrodes with Example.
o Draw Neat Diagram of calomel electrode with labeling.
o Explain Construction of Calomel electrode.
o Write electrode notation
o Working: Write Anodic and cathodic reactions.
10. What are ion selective electrodes? Derive equation of boundary
potential. Answer:
 Definition of Ion – Selective Electrode,
 Cell Scheme
 Derivation for boundary/membrane potential ( Eb).
11. Explain construction, working of Glass electrodes. Explain the advantages &
limitations of Glass electrode.
Answer:
 Draw neat diagram of glass electrode with labeling.
CBCS - BCHES202

 Draw neat diagram of glass electrode dipped in unknown solution with

labeling
 Explain construction, Glass composition, thickness, low M P, High
electrical
 Conductivity, limit of measuring pH and alkaline error.
 Explain Ion exchange process with reaction.
 Electrode notation.
 Derive equation for glass electrode; EG = E0G – 0. 0591 pH
 Write two advantages and limitations.

12. How is pH of a solution measured by using glass electrode?

Answer: Draw neat diagram-coupling calomel electrode and glass electrode dipped in
unknown solution whose pH is to be determined. Label the diagram.
 Explain Construct of cell assembly.
 Write cell notation.
 Derive equation for determination pH starting from the cell potential

E cell = ER – EL to pH =E0G – Ecal – Ecell

0.0591
13. What is Concentration cell? Explain construction, working and derivation of emf of
cell.
Answer: Definition of concentration Cell. Draw neat diagram with labelling, write cell
notation and reactions, explain Construct and working of cell. Derive emf of cell and
write conclusions.
14. What are potentiometry? Explain the principle, instrumentation and the application
of potentiometric sensor in the estimation of iron.
Answer: Definition of potentiometry, Explain principle, procedure, reactions, observation
and calculations with graph.
15. Explain the determination of strength of a weak acid using a conductometer.
Answer: Definition of conductometer, Explain principle, procedure, reactions, observation
and calculations with graph.

Even Semester 2022

-23