Module – 2 Corrosion and Electrode System

Introduction:
An electrode system is the heart of electrochemical devices, where chemical reactions occur, and electrons are
transferred.
Standard electrode potential (Eo)
It is the electrode potential when the electrode is in contact with a solution of unit concentration at 298 K, it is
denoted by Eo. If the electrode involves a gas then the gas is at 1 atm pressure.
Types of electrodes
(1) Metal-metal ion electrode
A metal-metal ion electrode is a type of electrode that consists of a metal in contact with a solution containing
its own ions.
Eg: Zinc-Zinc ion electrode (Zn2+)
(2) Gas electrode: A gas is in contact with an inert metal dipped in an ionic solution of the gas molecules. Eg.
Hydrogen gas electrode.
(3) Metal-metal insoluble salt electrode
A metal-metal insoluble salt electrode is a type of electrode that consists of a metal in contact with a sparingly
soluble salt of the same metal immersed in a solution containing common anion of the salt.
Eg: Calomel electrode (Mercury-Mercury chloride) (Hg/Hg2Cl2/Cl-)
(4) Ion selective electrode or membrane electrode: A membrane is in contact with an ionic solution. Eg: Glass
electrode
(5) Redox electrode: An inert metal dipped into a solution containing ions of two different oxidantion states. Eg:
Pt (Platinum)/Fe2+, Fe3+

Q**Imp** Define reference electrode. Outline the construction, working and applications of calomel
electrode.7M
Reference electrode:
A reference electrode is an electrode that has a stable and well-known electrode potential, used for the
determination of potentials of other electrodes in an electrochemical cell.
Calomel electrode:
The Calomel electrode, also known as the Saturated Calomel Electrode (SCE), is a reference electrode based on
the reaction between mercury (Hg) and mercury (I) chloride (Hg2Cl2) (calomel). It is widely used in
electrochemistry due to its stable potential and reversibility.
Construction: Hg, Hg2Cl2, KCl(Sat)
 Mercury pool: A small pool of mercury at the bottom of the electrode.
 Calomel paste: A mixture of Hg2Cl2 (calomel) and Hg, in contact with the mercury pool.
 Saturated KCl solution: A solution of potassium chloride, saturated with KCl, surrounding the calomel
paste, often used as the electrolyte.

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 Module – 2 Corrosion and Electrode System

Figure 1. Calomel Electrode

Working
Depending upon the nature of the other electrode of the cell, the calomel electrode can act as anode or cathode.
 When it acts as anode the electrode reaction is oxidation as follows

 When it acts as cathode, the electrode reaction is reduction as follows

 The net reversible electrode reaction is

Hg₂Cl₂(s) + 2e⁻ 2Hg(l) + 2Cl⁻ → (calomel)
Equilibrium: The reaction reaches equilibrium, establishing a stable potential.
Therefore, Ecal = EO - 0.0591 log [Cl-] at 25oC
The potential of calomel electrode vary with the concentration of KCl solution used. When saturated KCl is
used the potential is +0.241 V, for 1 M and 0.1 M KCl the values are +0.28 V & +0.334 V respectively.
Applications:
 It is used for the measurement of single electrode potential.
 It is used as reference electrode in all potential determination
 Electroanalysis: Measuring the concentration of analytes
 Corrosion monitoring: Tracking the corrosion potential of materials
 Electrochemical synthesis: Controlling the potential for chemical reactions
 Electroplating: Monitoring the potential during electroplating processes
Advantages:
 It is simple to construct
 The cell potential is reproducible and stable for a long period, so commonly used in all potentiometric
determination
 Cell potential doesn’t vary temperature.
Disadvantages:
It is cannot be used above 50oC, because Hg2Cl2 breaks down yielding unstable readings and it is toxic.

Q**Imp**Define ion selective electrode. Outline the construction and working mechanism of glass
electrode. Glass electrode with a neat diagram. 8M
Ion-Selective Electrode
An Ion-Selective Electrode (ISE) is a type of sensor that measures the activity or concentration of specific ions
in a solution and develops a potential. It is designed to respond selectively to a particular ion, while ignoring
others.
Glass electrode
A glass electrode is a type of ion-selective electrode used to measure the pH of a solution. It consists of a thin
glass membrane that is sensitive to hydrogen ions (H+).
Construction:
 Glass membrane: A thin, fragile glass membrane made from a specific glass with high electrical
conductivity and low melting point that is sensitive to hydrogen ions (H+).
 Internal reference electrode: A silver/silver chloride (Ag/AgCl) electrode immersed in a 0.1 M HCl.
 Internal solution: The glass bulb is filled with 0.1 M HCl.
The glass electrode is represented as Ag/AgCl(s)/0.1M HCl/glass membrane.

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 Module – 2 Corrosion and Electrode System

Figure 2. Glass electrode

Working: The mechanism steps are as follows, the glass surface gets hydrated both on the outside and inside.
H+ ions get absorbed on the hydrated layer.
The glass electrode works by exchanging hydrogen ions (H+) in the solution with sodium ions (Na+) in the glass
membrane, generating a potential difference that is proportional to the pH of the solution.
+ -
H+ (soln) + Na Gl (membrane) Na+ (soln) + H+Gl- (membrane)

The exchange of ions between the inner and outer membranes generates a boundary potential (EB).
The difference in H+ ion concentration between the two solutions drives the development of the boundary
potential.
Therefore, EB = E2 – E1
Where, E2 and E1 are the potentials developed at external and internal surface respectively
Hence, EB = EO + – [EO + ]
O
[Inner & outer membranes are identical, E get cancelled and n=1, C1=0.1 M and
EB = 0.0591 log C2 - 0.0591 log C1 (where L= - 0.0591 log C1 and C2=H+)
EB = L + 0.0591 log H+ (where pH= -log [H+])
EB = L – 0.0591 pH
The potential of the glass electrode EG, has three components
(a) The boundary potential
(b) The potential of internal Ag-AgCl reference electrode
(c) Small asymmetry potential
Asymmetry potential is a small potential arises due to the manufacturing imperfections.
EG = Eb + EAg/AgCl + Easy
EG = L - 0.0591 pH + EAg/AgCl + Easy
EG = EGo - 0.0591 pH, (Where EGo = L + EAg/AgCl + Easy)
Determination of pH using glass electrode
To measure the pH of a solution, in a pH meter, the glass electrode is combined with a saturated calomel
electrode (SCE) and it is immersed in the solution whose pH is to be determined.
The cell is represented as Hg(l)|Hg2Cl2(s)|KCl|solution|glass membrane|HCl(0.1M)|AgCl(s)|Ag(s)
The emf of the so formed cell is determined potentiometrically.
Ecell = ERight – ELeft = EGE – ECE
Ecell = EGo – 0.0591 pH –ECE
0.0591 pH = EGo – ECE - Ecell

Applications: Glass electrodes are widely used in various industries, including:

 It measure pH in various solutions

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 Module – 2 Corrosion and Electrode System

 It monitors pH in water treatment processes

 It measure pH in food processing to ensure product quality and safety.
 It monitors pH in pharmaceutical manufacturing, quality control, and research.
 It measure pH in blood, urine, and other bodily fluids to diagnose and monitor various medical
conditions.

Concentration cells
A concentration cell is an electrochemical device that consists of two half-cells with identical electrodes and
electrolytes, but differing concentrations of either the metal or the metal ion solution. This difference in
concentration generates a potential difference between the two half-cells.
Construction: Consider a concentration cell, as depicted in Figure 4. In this electrolyte concentration cell, the
metal rod in the dilute solution (C1) serves as the anode, while the metal rod in the concentrated solution (C2)
acts as the cathode.

Figure 3 Concentration cell

Cell representation M | Mn+ (C1) || Mn+ (C2) | M
For example, Cu | Cu2+ (0.1 M) || Cu2+ (0.5 M) | Cu

Q**Imp**Derive an expression for concentration cells.

Working:
The electrode in contact with the solution of lower concentration (C1) acts as the anode
Cu → Cu2+ (C1) + 2e- (Anode)
In contrast, the electrode in contact with the solution of higher concentration (C2) acts as the cathode
Cu2+ (C2) + 2e- → Cu (Cathode)
The net cell reaction
Cu2+ (C2) → Cu2+ (C1) (Net cell reaction)
This indicates that the concentration cell operates until the concentrations of the two solutions become equal.
The emf of the cell is given by: ECell = ECathode - EAnode

OR

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 Module – 2 Corrosion and Electrode System

Problems on concentration cell

1. A concentration cell was constructed by immersing two silver electrodes in 0.05 M and 1 M silver nitrate
solutions. Give the cell representation, cell reactions and calculate the emf of the cell.
Cell representation: Ag|Ag+ (0.05M) || Ag+ (1M) |Ag
Cell reactions: At anode: Ag→Ag+ + e-
At cathode: Ag+ + e- → Ag
Net cell reaction: Ag+ (1M) → Ag+ (0.05M)

= 0.076 V
2. The cell potential of copper concentration cell, Cu|CuSO4 (0.005M) ||CuSO4 (X M) |Cu is 0.0295 V at 25°C. Calculate
the value of X.

X=9.94 x 0.005

X= 0.05M

3. The cell potential of Ag concentration cell, Ag|Ag+ (0.002M) || Ag+ (X M) |Ag is 0.0751 V at 25 °C. Write the cell
reactions and calculate the value of X.
At anode: Ag→Ag+ + e-
At cathode: Ag+ + e- → Ag
Net cell reaction: Ag+ (X M) → Ag+ (0.002M)

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 Module – 2 Corrosion and Electrode System

X=18.65 x 0.002

X= 0.0373 M

4. Find the valency of the mercurous ions with the help of the following cell, Hg| 0.001 N HgNO3 in 0.1 N
HNO3|| 0.01 N HgNO3 in 0.1 N HNO3| Hg, when the emf is measured at 18 °C is 0.029 V.

n=1.992

5. Calculate the concentration of dilute solution of following concentration cell.

Zn|Zn2+ (C1) || Zn2+ (0.1 M)| Zn at 298 K, Ecell=0.0296 V.

C1= 0.01 M

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 Module – 2 Corrosion and Electrode System

Corrosion Chemistry
Corrosion is a naturally occurring process that involves the deterioration or degradation of materials, typically
metals, due to a chemical or electrochemical reaction with their environment. Eg: Rusting of iron, tarnishing of
silver, and patina formation on copper
Electrochemical corrosion (Wet corrosion)
Electrochemical corrosion occurs in environments where metals are exposed to water, moisture, or humid air.
This process involves electrochemical reactions between the metal surface, water, and atmospheric oxygen,
leading to corrosion.

Q**Imp** Define corrosion. Explain electrochemical theory of corrosion by taking iron as example. 5M
Electrochemical theory of corrosion (Wet corrosion) (reactions are important/mandatory to write)
Wet corrosion usually occurs in the presence of aqueous phase.

 The corrosion process involves the formation of large number of tiny galvanic cell, where anodic and
cathodic regions develop on the same metal surface.
 Corrosion (oxidation) takes place at the anodic region. The electrons released at the anode are absorbed at
the cathode, constituting the corrosion current.
Fe → Fe2+ + 2e- (Anodic reaction)
 The cathodic reaction in corrosion processes varies depending on the characteristics of the surrounding
environment
a) In aerated and neutral environments:
O2 + 2H2O + 4e- → 4OH-
b) In de-aerated and neutral environment:
2H2O + 2e- → H2 + 2OH-
c) In de-aerated and acidic environment:
2H+ + 2e- → H2
The iron ions (Fe2+) at the anodic areas react with hydroxide ions (OH-) to form iron hydroxide (Fe(OH)2),
which eventually leads to the formation of rust (Fe2O3·nH2O):
2Fe2+ + 4OH- → 2Fe(OH)2
2Fe(OH)2 + O2 (excess) + n. H2O → Fe2O3·nH2O (Rust)
In the presence of limited oxygen, black rust is formed as follows:
3Fe(OH)2 + (1/2) O2 (limited) → Fe3O4 .3H2O (Black rust)
Types of Corrosion
1. Uniform Corrosion: Even material loss across the surface.
2. Pitting Corrosion: Localized material loss, forming small holes or pits.
3. Crevice Corrosion: Corrosion occurring in confined spaces or crevices.
4. Galvanic Corrosion: Corrosion caused by contact between dissimilar metals.
5. Stress Corrosion Cracking (SCC): Cracking due to a combination of stress and corrosion.

Q**Imp** Write a Brief Note on the following (i) Differential metal corrosion. (ii) Sacrificial anode
method 8M
Differential metal Corrosion or Galvanic Corrosion (reactions are important/mandatory to write)
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 Module – 2 Corrosion and Electrode System

Differential metal corrosion, also known as galvanic corrosion, occurs when two dissimilar metals are in contact
with each other in the presence of an electrolyte, such as water or moisture.

The metal with a lower electrode potential becomes the anode, corroding more quickly, while the metal with a
higher electrode potential becomes the cathode, remaining protected from corrosion. The rate of corrosion is
directly proportional to the difference in electrode potential between the two metals.
Eg: A copper pipe connected to a steel pipe in a plumbing system.
In this example, when iron (electrode potential: -0.44V) comes into contact with copper (electrode potential:
+0.34V), iron, being higher up in the electrochemical series, acts as the anode and corrodes. In contrast, copper,
being lower in the series, is protected from corrosion and acts as the cathode.
 The steel pipe (anodic) starts to corrode, releasing electrons (e-) and forming iron ions (Fe2+).
 The copper pipe (cathodic) receives the electrons and remains protected from corrosion.

Q**Imp**What is differential aeration corrosion and discuss pitting corrosion as an example.

Differential aeration corrosion (reactions are important/mandatory to write)
Differential aeration corrosion, also known as oxygen concentration cell corrosion, occurs when a metal is
exposed to varying levels of oxygen (O2) in the environment. This creates an electrochemical cell, where the
area with higher oxygen (O2) levels becomes the cathode, and the area with lower oxygen (O2) levels becomes
the anode.

In a partial immersion scenario (Figure), the part of the metal exposed to lower oxygen concentrations acts as the
anode, while the part exposed to higher oxygen concentrations acts as the cathode. This is because oxygen has a
greater tendency to absorb electrons, driving the corrosion reaction. The resulting corrosion cell leads to
accelerated corrosion at the anodic areas, while the cathodic areas remain protected.

Pitting corrosion (reactions are important/mandatory to write)

Pitting corrosion is a type of localized corrosion that occurs on metal surfaces, resulting in small, deep holes or
pits. Pitting corrosion occurs when
 A small crevice or particle, such as dust, oil, water droplet settles on the metal surface creates a
localized area with low oxygen levels (anode).
 The surrounding area with higher oxygen levels becomes the cathode.
 An electrochemical cell forms, driving the corrosion reaction
 The pit grows as the corrosion reaction continues, often rapidly.

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 Module – 2 Corrosion and Electrode System

Figure. Pitting corrosion

Corrosion control
Corrosion control refers to the methods and techniques used to prevent corrosion damage to materials,
particularly metals.

Q**Imp** What is galvanization? Discuss the following corrosion prevention methods (i) galvanization
and (ii) Anodization. 8M
Galvanization is a corrosion protection process where a thin layer of zinc is applied to iron to prevent rusting.
The zinc layer acts as a sacrificial anode, protecting the underlying metal from corrosion.
Hot-Dip Galvanizing: Iron is dipped in a bath of molten zinc.
 Cleaning: Remove dirt, oil, grease, and other contaminants from the metal surface using a organic
solvent/degreaser.
 Pickling: Dip the metal in a dilute acid solution (usually dil. H2SO4) to remove scale, rust, and other
impurities.
 Rinsing: Rinse the metal thoroughly with water to remove any remaining acid solution.
 Fluxing: Apply a flux, typically a zinc ammonium chloride solution, to the metal surface to remove
oxides and promote zinc adhesion.
 Galvanizing: Dip the metal into a bath of molten zinc (around 460°C) for 3-5 minutes.
 Quenching: Remove excess zinc from the metal surface using a quenching.

Figure. Galvanization process

Galvanization is an effective way to protect steel and iron from corrosion, ensuring the longevity and reliability
of metal assets.

Q**Imp** What is surface conversion coating? Explain the steps involved in anodization process of
aluminium for corrosion control.
Surface conversion Coating:
Surface conversion coating, also known as chemical conversion coating, is a process that converts the surface of
a metal into a corrosion-resistant layer. This layer is formed through a chemical reaction between the metal
surface and a solution, resulting in a thin, protective coating.
Anodization (reactions are important/mandatory to write)

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 Module – 2 Corrosion and Electrode System

Anodization is an electrochemical process that converts the surface of aluminum into a durable, corrosion-
resistant layer of aluminum oxide. This process occurs in an electrolytic cell, as shown in Figure.

Figure. Anodization of aluminium

Electrode reaction
At anode (Oxidation) : 2Al(s) + 3H2O (l)  Al2O3 + 6H+ + 6e-
At cathode (Reductio : 6H+(aq) + 6e-  3H2(g)
Net cell reaction : 2Al(s) + 3H2O (l)  Al2O3 (s) +3H2 (g)
This process involves:
 Immersion in an electrolytic solution (10% H2SO4)
 Passage of an electric current through the solution
 Oxidation of the aluminum surface, creating a porous layer
 Sealing of the pores to enhance corrosion resistance
During anodization, an aluminum metal is used as the anode in an electrolytic bath containing a 10% H2SO4 acid
solution. A direct current is passed through the bath, causing the metal to oxidize and form a protective oxide
film.
In summary, anodization is a surface conversion coating process that creates a protective aluminum oxide layer
through electrolytic oxidation, providing corrosion resistance and a strong bond for paints and dyes.
Applications of Anodized Articles:
Anodization enhances the corrosion resistance and durability of aluminum, making it suitable for outdoor and
indoor applications.
What is sacrificial protection?
Sacrificial anode method
The sacrificial anode method is a technique used to protect metals from corrosion by using a more reactive
metal (the sacrificial anode) to divert the corrosive attack away from the protected metal.
This method protects base metals from corrosion by contacting them with more anodic metals like zinc (Zn),
magnesium (Mg), or aluminum (Al). These sacrificial metals have a lower standard electrode potential than the
base metal.

Figure. Sacrificial anodic protection

How it works:
 The sacrificial metal acts as the anode, corroding instead of the base metal.
 The base metal acts as the cathode, remaining protected from corrosion.
 The sacrificial anode is periodically replaced with a fresh block to maintain protection.
Eg: To protect copper (Cu) from corrosion, it is paired with zinc (Zn). Zinc lower standard electrode potential
makes it the anode, which corrodes, while copper is higher potential makes it the cathode, protecting it from
corrosion.

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 Module – 2 Corrosion and Electrode System

Applications:
This type of cathodic protection is used to safeguard:
 Buried pipelines
 Underground cables
 Water tanks
 Boilers
 Ships
Corrosion Penetration Rate (CPR)
Corrosion Penetration Rate (CPR) is a measure of the rate at which corrosion progresses through a material,
typically measured in units of depth per unit time.
A higher CPR indicates faster corrosion, while a lower CPR indicates slower corrosion.
Weight loss method for Measuring Uniform Corrosion
The Corrosion Penetration Rate (CPR) is calculated using the following formula:
CPR = (KW) / (ρAt)
Where: K = constant (534 for mils/year or 87.6 for mm/year) (1 mil= 0.001 inch) (1 inch= 2.54 cm)
W = total weight loss (mg)
t = exposure time (Hours)
A = exposed surface area (cm² for mmpy/inch2 for mpy)
ρ = specimen density (g/cm³)
This formula provides a quantitative measure of the corrosion rate, allowing for the evaluation of material
degradation and prediction of lifespan.

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. (Carbon steel
density=7.8g/ cm3).
Solution
Given CPR in mmpy CPR in mpy
K 87.6 534
W(wt loss) 40 g 40 x1000 mg 40 x1000 mg
3 3
(D)ρ 7.8g/cm 7.8g/cm 7.8g/cm3
A 1mx3m=3m2 3x100x100cm2 4650 inch2
T 6 months 6 x30x24 hrs 6 x30x24 hrs
CPR in mmpy
kxW
CPR 
D   x A x T
87.6 x 40 x 1000
CPR 
7.8 x 3 x 100 x100 x 6 x30 x 24
CPR  3.466 x 10 3 mmpy

CPR in mpy
kxW
CPR 
D   x A x T

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 Module – 2 Corrosion and Electrode System

534 x 40 x 1000
CPR 
7.8 x 4 650 x 6 x30 x24
CPR  0.1363 mpy

2. Calculate the CPR in both mpy and mmpy for a thick steel sheet of area100 inch2 which experiences a
weight loss of 485g after one year. (Density of steel=7.9g/cm3).
Solution
Given CPR in mmpy CPRinmpy
K 87.6 534
W(wt loss) 485 g 485 x1000 mg 485 x1000 mg
3 3
Ρ 7.9g/cm 7.9g/cm 7.9g/cm3
A 100 inch2 100 x6.45cm2 100 inch2
T 1year 365 x24 hrs 365 x24 hrs
CPR in mmpy
kxW
CPR 
D ρ  x A x T
87.6 x 485 x1000

7.9x 100 x 6.45 x365 x 24
 0.9518 mmpy

CPR in mpy
kxW
CPR 
D ρ  x A x T
534 x 485 x1000

7.9x 100 x 365 x 24
 37.42 mpy
2
3. A 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 8.73g/cm3.Calculate the CPR in
mm/year and mpy.
Solution
Given CPR in mmpy CPR in mpy
K 87.6 534
W(wt loss) 375 g 375 x1000 mg 375 x1000 mg
Ρ 8.73g/cm3 8.73g/ cm3 8.73g/ cm3
A 400 inch2 400 x6.45cm2 400 inch2
T 2year 2 x365x24 hrs 2 x365x24 hrs
CPR in mmpy
kxW
CPR 
D ρ  x A x T
87.6x 375 x1000

8.73 x 400 x 6.45 x 365 x 2 x 24
 0.083 mmpy
CPR in mpy
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 Module – 2 Corrosion and Electrode System

kxW
CPR 
D ρ  x A x T
534 x375 x1000

8.73 x 400 x 365 x2 x 24
 3.27 mpy

4. An iron plate found in a vessel containing acidic media, was estimated for an original area of 20 inch2 and
1.2 kg corrosion. Assuming a corrosion penetration rate of 400mpy for the iron in the acidic media, calculate
time in years, if density of iron 7.87g/ cm3.
Solution:
To calculate time in years
kxW
CPR 
D ρ  x A x T
kxW
T
D ρ  x A x CPR

Given CPR in mpy

K 534
W(wt loss) 1.2 kg 1.2 x1000x1000mg
3
ρ 7.87g/cm 7.87g/ cm3
A 20 inch2 20 inch2
t ?
CPR mpy 400 400
534 x 1.2 x 1000 x 1000
t
7.87 x 20 x 400
 10177.89 hrs
Converted in year
10177.89
t
365 x 24
 1.16 yrs
Analytical techniques
Q**Imp**Explain the conductometric estimation of acid mixture using standard NaOH
Conductometric titration can determine acids present in a mixture. For instance, titrating a mixture of HCl and
acetic acid (CH3COOH) with a strong base NaOH
Procedure:
Take 50 cm3 of the given acid mixture into a clean 100 cm3 beaker. Dip the conductivity cell in the solution and
note down the conductance of the solution i.e. when the volume of NaOH added is zero. Now add standard
NaOH solution from a burette in increments of 0.5 cm3. After each addition, stir the solution gently and note
down the conductance. As the titration proceeds, the conductance first gradually decreases and then rises slowly
and finally rises sharply. Continue titration until the conductance is more or less the same as it was in the
beginning. Draw a graph of conductance against volume of NaOH added. The point of intersection of the first
and the second lines give the volume of sodium hydroxide needed to neutralize only hydrochloric acid. The
point of intersection of the second and the third straight lines give the volume of NaOH required to neutralize
both HCl and CH3COOH (after drawing a perpendicular to X-axis).

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 Module – 2 Corrosion and Electrode System

Initial Decrease: Conductance decreases as highly mobile H+ ions are replaced by less mobile Na+ ions, until all
HCl is neutralized.
Moderate Rise: Further NaOH addition converts CH3COOH into CH3COONa, increasing conductance
moderately.
Sharp Rise: Excess NaOH increases conductance due to free OH- ions.
Graph Analysis:
Plot Volume of NaOH added against conductance.
Equivalence point Determination:
 Intersection of 1st and 2nd lines: Volume (V1) of NaOH neutralizing HCl.
 Intersection of 2nd and 3rd lines: Volume (V2) of NaOH neutralizing both HCl and CH3COOH.
Interpretation:

Figure. Nature of graph

Calculations:
Estimation of HCl :
NHCl = = ………….. N
Amount of HCl per dm3 of the solution = NHCl x 36.5 =……………… g/dm3
Estimation of CH3COOH :
NCH3COOH = = …………..
Amount of CH3COOH per dm3 of the solution = NCH3COOH x 60 =…………… g/dm3

Potentiometry
Q**Imp** Explain the potentiometric estimation of iron using standard K2Cr2O7 solution
Potentiometric estimation of iron using standard K2Cr2O7 solution involves titrating an iron sample with a
known concentration of potassium dichromate (K2Cr2O7) solution until the reaction is complete. The endpoint is
determined by measuring the potential difference between two electrodes.
Reaction:
Fe2+ (iron(II)) + Cr2O72- (dichromate) → Fe3+ (iron(III)) + Cr3+ (chromium(III))
Potentiometric Titration
Procedure: Pipette out 10cm3 of ferrous ammonium sulfate (FAS) solution into a 100 ml beaker. Add one test
tube full of dilute sulphuric acid. Immerse, the platinum - calomel electrode assembly in to the solution.
Measure the potential by adding standard K2Cr2O7 solution from the burette in increments of 0.5 cm3. Stir the
mixture for few seconds, and measure the potential of the solution after each addition. Plot a graph of ΔE / ΔV
against volume of K2Cr2O7 as shown in the figure. Find the equivalence point from the graph. Knowing the
equivalence point, calculate the normality of the FAS solution and determine the amount of FAS per liter of the
solution.
The equivalence point is indicated by a sharp change in potential.
Before the equivalence point: Fe2+ is present, and the potential remains relatively constant.
After the equivalence point: Fe3+ is formed, and the potential increases sharply.

Code: BCHES202 GSN

Course: Applied Chemistry for Computer Science & Engineering stream Department of Chemistry, NIE
14
 Module – 2 Corrosion and Electrode System

Calculations:
NFAS = = …………….N
Mass of FAS per dm = NFAS X 392 = (a) g/dm3
3

Figure. Nature of graph

Important Questions

1. Define reference electrode. Outline the construction, working and applications of calomel electrode.7M
2. Define ion selective electrode. Outline the construction and working mechanism of glass electrode.
Glass electrode with a neat diagram. 8M
3. A concentration cell was constructed by immersing two silver electrodes in 0.05 M and 1 M silver
nitrate solutions. Give the cell representation, cell reactions and calculate the emf of the cell.
4. Define corrosion. Explain electrochemical theory of corrosion by taking iron as example. 5M
5. Write a Brief Note on the following (i) Differential metal corrosion. (ii) Sacrificial anode method 8M
6. What is differential aeration corrosion and discuss pitting corrosion as an example.
7. Explain differential aeration corrosion with suitable examples and reactions. 6M
8. What are anodic metal coatings. Elucidate the steps involved in galvanisation with diagram. 6M
9. What is galvanization? Discuss the following corrosion prevention methods (i) galvanization and (ii)
Anodization. 8M
10. What is surface conversion coating? Explain the steps involved in anodization process of aluminium for
corrosion control.
11. 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. (Carbon
steel density=7.8g/ cm3).
12. Explain the conductometric estimation of acid mixture using standard NaOH
13. Explain the potentiometric estimation of iron using standard K2Cr2O7 solution

Code: BCHES202 GSN

Course: Applied Chemistry for Computer Science & Engineering stream Department of Chemistry, NIE
15