Department of Chemistry

Dayananda Sagar College of Engineering

MODULE 1
Corrosion and Electrode system
Corrosion Chemistry: Introduction
The destruction/deterioration of metals/alloys by the surrounding environment through
chemical/electrochemical changes. It is known as corrosion.
• The process of corrosion is transformation of pure metal into its undesired metallic compounds.
• Corrosion can be a fast/slow process depending upon the nature metal and the environment where
metal undergo corrosion.
Examples
1. Rusting of iron-Reddish brown color-Fe2O3.3H2O
2. Green color scale on copper –CuCO3+Cu(OH)2
Types of corrosion
1. Dry or direct chemical corrosion: Corrosion is due to direct chemical reaction between metal
and gases such as HCl, H2S, SO2, Cl2, F2, NH3 etc. present in environment in the absence of moisture
or conducting medium.
2. Wet or electrochemical theory of corrosion: Metal undergo corrosion in the presence of
moisture or conducting medium.
Electrochemical Theory of Corrosion
Metal undergo corrosion in the presence of moisture/conducting medium. It is known as
wet/electrochemical corrosion. “corrosion of metals takes place due to formation of anodic and cathodic
regions on the same metal surface/when two different metals are in contact with each other in the
presence of conducting medium”. Corrosion current-flow of electron from anode to cathode Corrosion
product deposit between anode and cathode

• Anodic region-Oxidation
• Cathodic region- Reduction

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Corrosion reactions
a) Anodic reaction- At the anodic area, oxidation take place, resulting in the corrosion of iron
1. Anode - M → Mn+ + ne-
Example: Fe → Fe2+ +2e-
2. At cathode- It’s depends on corrosion environment
Types of cathodic reactions
a. Liberation of hydrogen
(i) In Acidic medium- 2H+ +2e- → H2
(ii) In neutral/alkaline medium- 2H2O +2e-→ 2OH- + H2
b. Absorption of oxygen
(i) In Acidic medium- 2H+ + ½ O2 +2e- → H2O
(ii) In neutral/alkaline medium - H2O + ½ O2 +2e- →2OH-
RUST FORMATION
(i) In the presence of excess oxygen
Fe2+ + 2OH- → Fe(OH)2
2Fe(OH)2 + ½O2 + H2O →Fe2O3.3H2O (Reddish brown)
(ii) In the presence of limited oxygen
3Fe(OH)2 + ½O2 →Fe3O4.3H2O (Black colour)
Types of corrosion
According to electrochemical theory, corrosion occurs due to the formation of large number of galvanic
cells on the surface of the metal. A galvanic cell is formed, when there is a difference in potential between
the regions across the metal surface. It can happen in different ways.
1. Differential metal corrosion
When two dissimilar metals are in contact with each other in a corrosive conducting medium. The two
metals differ in their tendencies to undergo oxidation; the one with lower electrode potential or the more
active metal acts as anode and the one with higher electrode potential or the less active metal act as
cathode the potential difference between the two metals is the cause corrosion. The anodic metal under
goes corrosion and the cathodic metal is protected from corrosion.
When two metals Fe and Cu are in contact: Since iron has lower reduction potential compared to Cu,
iron undergoes corrosion and Cu is protected.

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Anodic reaction Cathodic reaction

Fe Fe 2+ + 2e- O2 + 2H2O + 4e- 4OH-

When two metals Zn and Fe are in contact: Since Zinc has lower reduction potential compared to Fe,
Zn undergoes corrosion and Fe is protected.

Anodic reaction Cathodic reaction

Zn Zn 2+ + 2e- O2 + 2H2O + 4e- 4OH-

Example: 1. Steel pipe connected to copper.

2. Zinc coating on mild steel.
3. Tin coating on copper vessels.

2. Differential aeration Corrosion

Corrosion of a metal due to difference in air or oxygen concentration on its surface is called differential
aeration corrosion. When a metal is exposedto different oxygen concentration. The part of the metal
exposed to higher oxygen concentration acts as cathodic region and the part of the metal exposed to
lower oxygen concentration acts as an anodic region. Consequently, the poor oxygenated region
undergoes corrosion. The reactions may be represented as follows:

More Aerated

Less Aerated

At anode : Fe → Fe2+ + 2 e- (oxidation)

At cathode : 1/2 O2 + H2O + 2 e- →2 OH- ( Reduction)

Fe2+ + 2 OH- → Fe(OH)2

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2Fe (OH)2 + 1/2 O2 + H2O → Fe2O3+ 3 H2O→ Fe2O3.3 H2O(rust)

Reactions
Example
1. Windows rods inside the frame suffer corrosion but not the exposed region.
2. Paper pins inside the paper gets corroded, and the exposed part is free from corrosion.

2a. Water-line corrosion

It is the differential aeration corrosion observed in iron or steel partially in contact with water. Usually
observed in water storage tanks, ship water lifting pipes etc. The portion under water will be exposed to
less concentration of oxygen and will act as the anode and undergo corrosion while the portion above
water act as cathode and will remain unaffected. The extent of corrosion will be maximum just below
the waterline and hence is called waterline corrosion. For example in water storage tank the metal tank
part inside water level exposed only to dissolved oxygen get corroded (anode) while the part above water
line is exposed to higher oxygen concentration is protected (cathode).

Fig: Water line corrosion

2b. Pitting corrosion
It occurs when small particles of dust, water drop on metal surface or breakdown of protective film. A
typical pitting corrosion is illustrated as shown in figure. The metal portion covered by dust act as anode
due to less oxygenated and undergoes corrosion beneath the dust forming a pit. The metal part free from
dust exposed to higher oxygen concentration become cathode and protected from corrosion. The
corrosion rate is higher in this case due to small anode area and large cathode area. All the electrons
liberated at anode (pit) are absorbed by large cathode area for reduction reaction.

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Fig : Pitting Corrosion
Factors affecting rate of corrosion
The rate of corrosion depends on the following factors.
a) Nature of Metal:
1. In general the metals with lower electrode potential values are more reactive than the metal with
higher electrode potential values,
2. The more reactive metals are more susceptible for corrosion, thus the tendency of metal to
undergoes corrosion decreases with increase in electrode potential. For example,
3. The active metals like k, Na, Mg, Zn etc, with low electrode potential values are highly
susceptible for corrosion.
4. The noble metal such as silver, gold, platinum etc, with higher electrode potential values are less
susceptible for corrosion. However, there are few exceptions for this general trend as some metal
show the property of passivity.
b) Nature of Corrosion Product- The rate of corrosion depends on the nature of corrosion product
which is formed during corrosion. In the case of metal like iron, zinc and magnesium, the oxides
which are formed during corrosion are, highly porous, non-stoichiometric, highly soluble and good
ionic conductivities, As a result, corrosion is continued till the metal is completely destroyed. On the
other hand, in the case of metal like aluminum, titanium, chromium etc, the oxides formed are non-
porous, stoichiometric, and highly insoluble with low ionic and electronic conductivities. As a result,
the corrosion is stopped as soon as oxide film is formed.
c) Relative size of the anodic and cathodic areas: Smaller the anodic area and larger the cathodic area,
then more intense and faster will be the corrosion at anodic area. When cathodic area is large, demand
for electrons for reduction reaction is high. To meet this demand, oxidation reaction occurs more
intensely at anodic area.
Ex: In case of coating tin on iron, if some area is not covered, a small anodic area and large cathodic
area are formed. In this case rate of corrosion of iron becomes higher than that under normal conditions.

On the other hand, if anodic area is large and cathodic area is small, then the rate of corrosion at anodic
area will be very low. In case of coating zinc on iron, if some areas are not covered, a small cathodic
and large anodic area are formed. In this case rate of corrosion of iron metal becomes lower.

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d) pH of the medium: In general, lower the pH of corrosion medium, higher is the corrosion rate.
(Exception: Metals like Al, Zn etc. undergo fast corrosion in media with high pH).Iron does not undergo
corrosion at pH greater than 10. This is due to the formation of protective coating of hydrous oxides of
iron. Between pH 10 and 3, the presence of oxygen is essential for corrosion. If the pH is less than 3,
severe corrosion occurs even in the absence of oxygen due to continuous evolution of hydrogen gas.
e) Temperature: In general increase in temperature increase in corrosion rate. For many metals
the corrosion rate almost exponentially rises with increase in temperature. This is attributed to
1. Increase in conductance of the medium- ions migrate fast at higher temperature.
2. Increase in the rate of chemical reaction
3. Increase in solubility of the corrosion products in the medium
4. Decrease in the polarization effects at the anode and cathode sites. However, if corrosion is due
to dissolved gases like O2, CO2 etc. The rate of corrosion decreases with an increase in temperature
as the solubility of these gases in the medium decreases.

Corrosion control
According to electrochemical theory, corrosion occurs due to the oxidation and reductions reactions at
the anodic and cathodic areas. These reactions occur simultaneously and are interdependent. So by
decreasing the rate of any of these reactions or by preventing any one reaction, the rate of corrosion can
be decreased. The methods used to control corrosion are:
1. Metal Coating
a) Anodic Metal Coating: Galvanisation
b) Cathodic Metal Coating: Tinning
2. Cathodic protection- Sacrificial Anode Method
3. Anodization
4. Corrosion inhibitors

1. Metal Coating
a) Anodic Metal Coating: Galvanisation: Anodic metal coatings are coatings which are anodic to
base metals. Example are Al, Zn etc. These metals are above the Fe in the galvanic series and undergo
corrosion thereby protecting Fe. A characteristics feature of anodic coating is that the base metal on
which the coating is done will not get corroded even if the coating peals off. This is due to formation of
large anodic area and small cathodic areas.
Example: Galvanisation: It is a process of coating Zn over the surface of iron. The method is carried
out by hot dipping process. It involves the following steps:
1. The iron sheet is washed with solvent to remove greasy & oily materials.

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2. The iron sheet is washed with dil H2SO4 to remove oxide film.
3. The sheet is then treated with a mixture of aqueous solution of zinc chloride and ammonium chloride
& dried
4. The dried sheet is dipped in molten zinc at 430 – 450 0 C.
5. Excess Zn is removed by rolling, wiping or air blast.

Fig: Galvanization process

Applications
1) Galvanized iron pipes are exclusively used for domestic purpose all over the world
2) Galvanized iron drum are used to preserve variety of chemicals, drugs & organic solvents.
3) Used in Roof sheets, fencing wires, barbed wire, buckets, pipes, etc.

2. Cathodic protection- Sacrificial Anode Method

Cathodic protection is a technique of offering protection to a specimen against corrosion by providing
electrons from an external source.
Sacrificial anode method:
Corrosion of metal occurs at anodic area, where metals are oxidized to metal ions. In cathodic protection,
electrons are supplied from an external source to reverse and prevent oxidation of metal at anodic area.
Thus anodic are will be converted to cathodic. The process of protecting a metal against corrosion by
making the entire metal cathodic by providing electrons from an external source is called cathodic
protection.
Examples:
1. Mg block connected to ships floating on water surface.
2. Mg block connected to underground buried pipe.

In this the metal structure to be protected is connected to a more anodic metal like Mg, Zn and Al which
acts as anodic. In practice active metal Mg or Zn is connected to metal structure to be protected. The
more active metal Mg or Zn becomes anodic and corrodes but the metal structure becomes cathodic is
protected. Since the anode metal sacrifices to protect the metal structure the method is known as
sacrificial anode method.

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Fig: Sacrificial Protection

The metallic structure to be protected is connected to a more anodic metal using a metallic wire. The
more active metal gets corroded, while the parent structure is protected from the corrosion. The more
active metal so employed is called sacrificial anode. As the anodic metal sacrifices its life to protect the
base metal from corrosion is called sacrificial anodic protection. The commonly used sacrifical anodes
are Mg, Zn, Al etc this method is generally used for the protection of buried pipe lines ship hulls, water
tanks.
Impressed voltage method: In this method, current is applied from apposite direction to nullify the
corrosion current and convert the corroding metal from anode to cathode, Usually, the impressed current
is derived from a direct current source with an insoluble anode (like graphite or platinum

Usually, a sufficient DC current is applied to an insoluble anode and buried pipe in the soil and connected
to the metallic structure to be protected (see the fig) to increase the electrical contact between the anode
and the soil, the anode is buried in a back fill such as gypsum under the earth. Thus electrons are supplied
from an external cell so that the object itself becomes cathodic and is not oxidized. This type of cathodic
protection has been applied to open water box cooler, water tanks, ships etc.

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. The
method used to measure the corrosion rate was Weight Loss Method. This method was used as a
measurement of the Corrosion Penetration Rate (CPR) which is expressed in mile per year (mpy) or
millimeter per year (mm /yr). Where the material density (ρ), testing time (t) and weight (W) are a parameter
which to is known during the testing process, the CPR can be calculated by the equation:
Corrosion penetration rate (CPR) = kW/ ρAt
Where,

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k = constant depends on unit used, when K = 534 the mpy will be used. When K = 87.6, mm/yr
will be used.
W = Weight loss during testing
ρ = density of metal
A= area exposed for corrosion
t = duration of corrosion

Numerical Problems:
1) An iron metal lost 2.4 х10 -3 g of weight when it is immersed in deaerated acidic solution for 2 hrs.
Calculate the corrosion penetration rate (CPR) for the exposed area of 4 cm2. Given k = 534 and the
density of metal = 5.37 g cm-3.
Solution:
Corrosion penetration rate (CPR) = kW/ ρAt
= 534 X 2.4 х10 -3
5.37 X 4 X 2
= 0.027 cm/hr

2) An iron metal lost 3.3 x 10-3 g of weight when immersed in deaerated acid solution for 3 hour.
Calculate the corrosion penetration rate for the exposed area of 5cm2. Given K=534 and density of metal
=5.37 g cm-3.
Corrosion penetration rate (CPR) = kW/ ρAt
= 534 X 3.3 х10 -3
5.37 X 5 X 3
= 0.022 cm/hr

Electrode system
Electrochemistry: It is a branch of chemistry which deals with the study of transformation of
chemicalenergy into electrical energy and vice versa”
Electrochemical cells: An electrochemical cell is a device which converts chemical energy into
electricalenergy or electrical energy into chemical energy”
Gibbs Free Energy (G): Gibbs energy is defined as maximum available energy in a system that can
beconverted into useful work.
G =H -TS
The thermodynamic free energy is the amount of work that a thermodynamic system can perform. The
free energy is the internal energy of a system minus the amount of energy that cannot be used to perform
work.
EMF of a cell Or Cell Potential : “Emf is the potential difference between the two electrodes of
a galvanic cell, which causes the flow of current from one electrode to other. It is also called as
cell potential or cell voltage. It is expressed in volts.
Mathematically,Ecell = Ecathode – Eanode
Ecell = Eright electrode – Eleft electrode

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Single electrode potential or half cell potential [E]:

The potential that is developed due to the tendency of an element (metal or non-metal) to lose or gain
electrons, when it is in contact with the solution containing its own ions is known as single electrode
potential.

Standard electrode potential [Eo]:

The potential that is develop when an element is in equilibrium with the solution containing its own ions
of unit concentration (1 M) at 298 K is known as standard electrode potential.

Types electrodes:
In Electrochemical work various type of electrodes are employed depending upon the purpose for which
they are used. Some of them are
1. Metal-Metal ion electrode: An electrode of this type consists of a metal dipped in a solution
containing its ions. Ex- Zn/Zn2+, Cu/Cu2+ etc.
The electrode rxn is, in general
Mn+ +ne- M
2. Metal-Metal insoluble salt electrode: These electrodes consist of a metal in contact with a
sparingly soluble salt of the same metal dipped in a solution containing anion of the salt.
Example-Calomel (Hg|Hg2Cl2|Cl-), Silver- Silver salt electrode (Ag| AgCl |Cl-).
3. Gas electrode: Gas electrode consists of a gas bubbling about an inert metal wire, immersed in
solution containing ions to which the gas is reversible. The metal provides electrical contact and
facilitates the establishment of equilibrium between the gas and its ions.
Example-Hydrogen electrode (Pt|H2|H+), Chlorine electrode (Pt|Cl2|Cl-).
4. Oxidation-Reduction electrode: An oxidation-reduction electrode is a one in which the electrode
potential arises from the presence of oxidized and reduced forms of the same substance in
solution. The potential arises from the tendency of one form changes into the other more stable
form. The potential developed is picked up by an inert electrode like platinum.
Example-Pt|Fe2+, Fe3+, Pt|Ce3+, Ce4+
5. Amalgam electrode: It is an electrode which consists of a metal-amalgam dipped in a solution
containing its own metal ions. It is similar to Metal-Metal ion electrode.
Example-Pb-Hg|Pb2+, Zn-Hg|Zn2+
6. Ion selective electrode: it is an electrode, which consists of a membrane and in contact with a
solution, with which it can exchange ions.
Example- Glass electrode.

ION SELECTIVE ELECTRODES

Ion selective electrode possess the ability to respond only to a specific ions, there by developing a
potential w.r.t that species in a mixture and ignoring the other ions totally.
For example: Glass electrode
Construction: The glass electrode consists of a glass bulb made up of special type of glass which has
low melting point and relatively high electrical conductivity. The glass bulb is filled with a solution of
constant pH (0.1MHCl) and insert with an Ag-AgCl electrode, which is the internal reference electrode
and also serves for the external electrical contact. The electrode is represented as, Glass|0.1M
HCl|AgCl(s), Ag(s).
The potential of glass electrode when dipped in a solution containing H+ ions, is given by
EG= E0G+ 0.0591 log [H+] (Since n = 1)

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Figure: Glass Electrode.

Principle: When a thin glass membrane is placed between two solutions of different pH values, a
potential difference arises across the membrane. The potential difference varies as the pH of these
solutions varies. In practice, pH of one of these solutions is kept constant and therefore the electrode
potential depends on pH of the other solution in the experimental solution.
The membrane undergoes an ion exchange reaction, the Na+ ions in the glass membrane are exchanged
for H+ ions.
H+ + Na+Gl - Na+ + H +Gl-
Solution membrane Solution membrane

Working: The Potential of the glass electrode is sum of 3 potentials, boundary potential (Eb), inner
reference electrode (EIRE) and asymmetric potential (Easy).
𝐸𝐺 = 𝐸𝑏 + 𝐸𝐼𝑅𝐸 + 𝐸𝑎𝑠𝑦

2.303𝑅𝑇 𝐶1
Where, 𝐸𝑏 = 𝐸1 − 𝐸2 = 𝑙𝑜𝑔
𝑛𝐹 𝐶2
+
𝐶1 =Concentration of H of solution to be analyzed
𝐶2 =Concentration of H+ in the internal standard electrode
2.303𝑅𝑇 𝐶1
⸫ 𝐸𝐺 = 𝑛𝐹 𝑙𝑜𝑔 𝐶2 + 𝐸𝐼𝑅𝐸 + 𝐸𝑎𝑠𝑦
𝐸𝐼𝑅𝐸 𝑎𝑛𝑑 𝐸𝑎𝑠𝑦 are constants called standard reduction potential at glass electrode (𝐸𝐺0 )
2.303𝑅𝑇
𝐸𝐺 = 𝐸𝐺0 + 𝑛𝐹 𝑙𝑜𝑔𝐶
when, C1=[H+] and ∆C2=0
2.303𝑅𝑇
𝐸𝐺 = 𝐸𝐺0 + 𝑛𝐹
𝑙𝑜𝑔[𝐻 + ]

2.303𝑅𝑇
𝐸𝐺 = 𝐸𝐺0 − 𝑛𝐹
pH

𝐸𝐺 = 𝐸𝐺0 − 0.0591𝑝𝐻

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DETERMINATION OF pH USING GLASS ELECTRODE

Figure: Determination of pH using glass electrode.

To determine the pH of the given solution the glass electrode is dipped into the solution. It is combined
with a reference electrode such as a calomel electrode through a salt bridge. The cell assembly is
represented as,
Pt, Hg|Hg2Cl2|Cl-||Solution of unknown pH|glass|0.1M HCl| Ag, AgCl
The emf of this cell is determined using potentiometer. The emf of the cell is given by.
Ecell = Ecathode - Eanode
Ecell = Eglass - ESCE
Ecell = Eo-0.0591 pH - ESCE (since 𝐸𝐺 = 𝐸𝐺0 − 0.0591𝑝𝐻 and n=1)
By Rearranging the above equation we obtain,
0.0591pH = Eo - Ecell – ESCE
pH = Eo - Ecell – ESCE
0.0591
pH = Eo - Ecell – 0.2422
0.0591

Reference electrode
“Reference electrode is an electrode whose potential is known and with reference to that, the electrode
potential of any electrode can be measured”. There are two types of reference electrodes. They are
primary and secondary reference electrodes. Primary Reference Electrode: It is an electrode, whose
potential is arbitrarily taken as zero at all temperatures. Eg- Standard Hydrogen Electrode (SHE)

Calomel electrode: It is a secondary reference electrode.

Figure: Calomel Electrode

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Construction:
It consists of glass tube having a side tube at each end. A small amount of pure mercury is placed
at the bottom of the glass tube and covered by a calomel paste obtained by grinding together Hg,
Hg2Cl2 and either 0.1N KCl or 1NKCl or saturated KCl. The remaining portion is filled with either
0.1N KCl or 1NKCl or saturated KCl solution. Platinum wire is dipped into the mercury layer and
is used for making electrical contact. The side tube is used for making electrical contact with a salt
bridge.
Calomel electrode can be represented as, Hg(s)/Hg2Cl2(liq)|Cl-.
Working:
Reactions: The electrode behaves either as anode or as cathode
When it behaves as anode, the electrode reaction is:
2Hg (l) + 2Cl- → Hg2Cl2(s) + 2e
When it behaves as cathode, the electrode reaction is:
Hg2Cl2(s) + 2e→2Hg (l) + 2Cl-
Net half cell reaction is represented as Hg2Cl2 + 2e- 2Hg + 2Cl-

Nernst equation for calomel electrode: Ecal = E0cal – 0.0591 log [Cl-] at 298 K

Hence, the electrode potential of Calomel electrode dependent on the concentration of chloride ions

Concentration of KCl 0.1N 1.0N Saturated

Potential of Calomel Electrode 0.338 V 0.281 V 0.244 V

Advantages:
• It is very simple construction.
• It can be used for long time without much attention.
• Its electrode potential will not vary with temperature.
• It is used as reference electrode.

Concentration cells
The cells in which the EMF produced is due to the difference in the concentrations of the electrodes or
electrolytes.
There are two types of concentration cells.
i) Electrode concentration cells: A cell is formed by combination of same electrodes of different
concentrations dipped in same electrolyte solutions is called electrode concentration cell.
For example: Pt, H2 (1atm) ǀ H+(1M)ǀǀ H+(1M)ǀ H2(2 atm),Pt
ii) Electrolyte concentration cells: A cell is formed by combination of same electrodes dipped in same
electrolyte solutions of different concentration is called electrolyte concentration cell.
For example: Cu(s) / Cu2+ (C1) // Cu2+ (C2) / Cu(s) Where C2 > C1
EMF of a concentration cell: Consider a concentration cell
M / Mn+ (C1) // Mn+ (C2) / M Where C2 > C1
Anode Cathode
E cell = E Cathode – E anode

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Figure: Concentration Cells.

Applying Nernst equation for single electrode potential, we get

logC2 − E Mn logC1
0.0591 0.0591
+/ M + +/ M −
0 0
Ecell = E Mn
n n
logC2 − logC1
0.0591 0.0591
Ecell =
n n
0.0591 [C 2]
Ecell = log
n C1
This is the expression of Nernst equation for concentration cell at 25C.

Numerical Problems:
1. A concentration cell was constructed by immersing two silver electrode in 0.05 M and 1M of
AgNO3 solution. Write the cell representation and calculate the Ecell at 298K.
Solution: AgǀAgNO3 (0.05M)ǀǀAgNO3 (1M)ǀAg
0.0591 𝐶2
Eg= 𝑛 log𝐶1
0.0591 1
= log0.05 = 0.0768 V
1

2. Represent the cell formed by coupling two Cu-electrode immerses in CuSO2 solution
concentration of Cu2+ ions in one electrode system and 100 times more concentrated than other.
Calculate the Ecell at 298K
Solution : CuǀCu2+ (1M)ǀǀCu2+ (100M)ǀCu
0.0591 𝐶2
Eg= 𝑛 log𝐶1
0.0591 100
= log = 0.0591 V
2 1

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