2018-2019

ELECTROCHEMISTRY
(Lecture Notes)
WEIGHTAGE IN XII BOARD EXAMS: 5 MARKS
 CONTENTS
1. Introduction.
2. Electrolysis
(i) Product of electrolysis.
(ii) Faradays laws of electrolysis.
3. Conductance in electrolytic solutions
(i) Specific conductance.
(ii) Molar conductance.
(iii) Equivalent conductance.
4. Variation of conductivity with concentration.
5. Kohlrausch’s law.
6. Electrode potential
(i) Standard electrode potential.
(ii) Standard Hydrogen Electrode.
(iii) Determination of electrode potential.
(iv) Electrochemical series.
7. Galvanic cell
(i) Representation of galvanic cell.
(ii) EMF of galvanic cell.
(iii) Prediction of occurrence of a redox reaction.
(iv) Work done by the cell.
8. Nernst equation
(i) Nernst equation for potential of single electrode.
(ii) Nernst equation for EMF of cell.
9. Concept of Equilibrium in electrochemical cell.
10. Concentration cells.
(i) Electrode concentration cell.
(ii) Electrolyte concentration cell.
11. Metal-insoluble metal salt-anion half cell.
12. Relationship between electrical energy and enthalpy of a cell reaction.
13. Commercial Cells and Batteries.
(i) Primary cells.
(ii) Secondary cells.
(iii) Fuel cells.
14. Theory of corrosion.
Page 2 of 69
INTRODUCTION
“Electrochemistry is the branch of physical chemistry which deals with the interdependence of chemical
change and electrical energy.”

Electrochemistry is broadly divided into two categories:

➢ Production of chemical change by electrical energy (phenomenon of electrolysis).

➢ Conversion of chemical energy into electrical energy. i.e. generation of electricity by spontaneous
redox reactions.

ELECTROCHEMICAL CELLS
“Electrochemical cell is defined as a system consisting of two metallic electrodes, dipping into same or
different electrolytes, in electrical communication.”

Electrochemical cells are divided into two main types:

➢ Electrolytic cell.
➢ Galvanic or voltaic cell.

ELECTROLYTIC CELL
“An electrolytic cell is an electrochemical cell in which an electric current drives a non-spontaneous redox
reaction (∆G= +ve).”
“The process of producing a chemical change in an electrolytic cell is called electrolysis.”

GALVANIC (or) VOLTAIC CELL

“A voltaic or galvanic cell is an electrochemical cell in which a spontaneous redox reaction generates
electric current.”
The driving force in a galvanic cell is decrease in free energy (∆G), which may be due to chemical change or
physical change.

Galvanic cells is of two types:

➢ Chemical or Formation cell.

➢ Concentration cell.

CHEMICAL (or) FORMATION CELL

“It is the galvanic cell in which electrical energy is produced due to a chemical change occurring within
the cell.”

CONCENTRATION CELL

“It is the galvanic cell in which electrical energy is produced due to physical changes taking place within
the cell.”
It involves transfer or matter from one part of cell to another.

Page 3 of 69
 Electrochemical cells

Galvanic cells Electrolytic cells

Chemical cells Concentration cells

ELECTROLYSIS
“The process of chemical decomposition of an electrolyte by passage of electric current through its solution
is called electrolysis.”
or
“Chemical change (oxidation and reduction) occurring at electrodes when electric current is passed through
electrolytic solution is called electrolysis.”

The device in which electrolysis (chemical reaction involving oxidation and reduction) is carried out by
using electricity or the device in which conversion of electrical energy into chemical change is done is known
as electrolytic cell.

An electrolytic cell consists of a vessel for the electrolytic solution or fused electrolyte and two metallic
electrodes are immersed in the reaction material which are connected to a source of electric current.

The metallic electrodes which do not react with ions or final products are called inert electrodes.
Inert electrodes are usually used in an electrolytic cell.

Molecules of an electrolyte when dissolved in water split up into ions, i.e. into cations and anions.

On passing current, these ions move towards oppositely charged electrodes.

On reaching the electrodes the ions lose their charge either by accepting electrons or losing electrons and
thereby get deposited at the respective electrodes or undergo a secondary change.

The conversion of ions to neutral particles at the respective electrodes is referred to as primary change. The
product obtained on primary change may be collected as such or may undergo secondary change.

Page 4 of 69
For example, when electric current is passed through a solution of hydrochloric acid, the H+ ions move
towards cathode and Cl- ions move towards anode.
HCl   H+ + Cl-
Cathode (Reduction) Anode (Oxidation)
H + e 
+ -
H .
Cl-   Cl. + e-
2 H.   H2 2 Cl.   Cl2

The decomposition of HCl into H2 and Cl2 as a result of passage of current is termed electrolysis of HCl. It is,
thus, a process in which electric current brings the chemical change.

PREFERENTIAL DISCHARGE THEORY

If an electrolytic solution consists of more than two ions, it is observed that all the ions are not discharged at the
electrodes simultaneously but certain ions are liberated at the electrodes in preference to others.
This is explained by Preferential Discharge Theory.

“Preferential discharge theory states that if more than one type of ions is attracted towards a particular
electrode, then the one discharged is the ion which requires least energy.”

“The potential at which the ion is discharged or deposited on the appropriate electrode is termed the
discharge or deposition potential.”

The values of discharge potential are different for different ions.

ELECTROLYSIS OF COPPER SULPHATE SOLUTION USING COPPER ELECTRODES

The electrolysis of an aqueous solution of copper sulphate using copper electrodes (i.e. using active electrodes)
results in transfer of copper metal from the anode to the cathode during electrolysis.

The copper sulphate is ionized in aqueous solution as,

CuSO4   Cu 2+ +SO2-4
The positively charged copper ions migrate to the cathode, where each copper ion gains two electrons to
become copper atoms and are deposited on the cathode.
Cu 2+ +2e  Cu
At the anode, each copper atom loses two electrons to become copper ions, which go into solution.
Cu   Cu 2+ +2e

The sulphate ion does not take part in the reaction and the concentration of the copper sulphate in solution
does not change. The reaction gets completed when the anode is completely eaten away.

ELECTROLYSIS OF COPPER SULPHATE SOLUTION USING PLATINUM ELECTRODES

An aqueous solution of Copper (II) sulphate contains four types of ions: Cu2+ and SO2-4 ions from CuSO4 and
H+ and OH- ions from H2O .

At the anode:
OH- ions and SO2-4 ions are attracted to the anode. OH- ions give up electrons more readily than SO2-4 ions, as
OH- have lower discharge potential than SO2-4 ions. Consequently, OH- ions are preferentially discharged to give
oxygen gas.

Page 5 of 69
 4OH-(aq) 
 2H2O(l) +O2(g) +4e
The SO2-4 ions remain in solution.

At the cathode:
H+ ions and Cu2+ ions are attracted to the cathode. Cu2+ ions have lower discharge potential than H+ ions, hence
Cu2+ ions accept electrons more readily than H+ ions. As a result, Cu2+ ions are preferentially discharged as
copper metal (atoms).
Cu 2+ (aq) +2e 
 Cu (s)
The H+ ions remain in solution.

When an aqueous solution of CuSO4 is electrolyzed using platinum electrodes, copper metal is deposited at
the cathode and oxygen gas is given off at the anode.

Overall reaction:
2CuSO4 aq +2H2Ol 
 2Cus +O2g +2H2SO4 aq

During electrolysis, the cathode is coated with a layer of reddish-brown solid copper. The blue colour of the
solution fades gradually as more copper is deposited. The resulting electrolyte becomes increasingly acidic.

ELECTROLYSIS OF MOLTEN SODIUM CHLORIDE

The Na+ ions flow toward the negative electrode and the Cl- ions flow toward the positive electrode.

At the Cathode (negative electrode):

Na + +e 
 Na
At the Anode (positive electrode):
2Cl- 
 Cl2 +2e
Overall reaction:
2NaCl 
Electrolysis
 2Na + Cl2

ELECTROLYSIS OF AQUEOUS SOLUTION OF SODIUM CHLORIDE

The solution of sodium chloride besides Na+ and Cl- ions possesses H+ and OH- ions due to ionization of water.
When potential difference is applied across the two electrodes, Na+ ions move towards cathode and Cl- ions
move towards anode.

There are two substances that can be reduced at the cathode: Na+ ions and water molecules.
At the Cathode:
Na + +e   Na ;E0red =-2.87V
2H2O + 2e 
 H2 + 2OH- ;E0red =-0.83V

Since, the standard reduction potential for the reduction of water molecules is higher than the standard
reduction potential for sodium ions, the only product formed at the cathode is hydrogen gas.

There are also two substances that can be oxidized at the anode: Cl- ions and water molecules.
At the Anode:
2Cl-  Cl2 +2e ;E0ox = -1.36V
2H2Ol 
 O2 g + 4H+ + 4e ;E0ox =-1.23V

Page 6 of 69
It would be expected to observe water getting oxidized (Eoox = -1.23 volts) than Cl- ions (Eoox = -1.36 volts).
But in real, the oxidation of Cl- ions is rather observed due to a phenomenon known as overvoltage.

“Overvoltage is defined as the extra voltage that must be applied to a reaction to get it to occur at the rate at
which it would occur in an ideal system.”
Electrolysis of aqueous NaCl solutions gives a mixture of hydrogen and chlorine gas and an aqueous sodium
hydroxide solution.
2NaClaq +2H2Ol 
Electrolysis
 2Na +aq +2OH-aq  +H2g  +Cl2g 

The Na+ and OH- ions remain in solution and the solution when evaporated yields crystals of sodium hydroxide.

ELECTROLYSIS OF DILUTE SULPHURIC ACID

Sulphuric acid is a strong electrolyte is fully dissociated in aqueous solution.

H2SO4   2H+ +SO42-aq
Water is a weak electrolyte and is only slightly dissociated.
H2O l  H+aq +OH-aq 
During electrolysis, the hydrogen ions migrates towards the cathode, and are discharged there (i.e. they gain an
electron and are converted to hydrogen gas).
2H+ aq +2e 
 H2 g 
At anode the concentration of sulphate ions is too low to maintain a reaction, hence, though the oxidation
potential for sulphate ion is higher than for water molecules, sulphate ions will not be preferentially
discharged on account of their low concentration.
2H2Ol   4H+aq +O2g +4e ;Eox
0
=1.23V
2SO2-4  aq 
S2O82-aq  +2e ; E0ox =1.96V

Note:
At higher conc. the oxidation of sulphate ion will be preferred at anode.

Overall Cell Reaction:

4H+ aq + 2H2Ol 
 2H2g +O2g +4H+aq 
For every hydrogen ions discharged at the anode, another hydrogen ion is formed at the cathode.
The net result is that the concentration of the sulphuric acid remains constant and this electrolysis consists
of the decomposition of water with the overall reaction.
2H2Ol  2H2g  +O2g 

FARADAY’S LAWS OF ELECTROLYSIS

Faraday’s laws give the quantitative relationship between the quantity of electric charge passed through an
electrolyte and the amount of the substance deposited at the electrodes.

FARADAY’S FIRST LAW

According to Faraday’s First Law,

“The amount of substance discharged is proportional to the quantity of electric charge passed through the
electrolyte.”

If ‘m’ be the mass of the substance discharged by passing ‘Q’ coulomb of charge, then according to the law,

Page 7 of 69
we have the relation:
mαQ
A coulomb is the quantity of charge when a current of one ampere is passed for one second.

Thus, amount of charge in coulombs, Q = Current in amperes × Time in seconds

=I×t
 mαI×t
 m=Z×I×t

where, Z is a constant, known as electrochemical equivalent, and is characteristic of the substance deposited.

When a current of one ampere is passed for one second, i.e. one coulomb charge is passed, then m = Z

“Electrochemical equivalent can be defined as the mass of the substance deposited by one coulomb of
charge or by one ampere of current passed for one second.”

For example, when a charge of one coulomb is passed through silver nitrate solution, the amount of silver
deposited is 0.001118 g. This is the value of electrochemical equivalent of silver.

Again according to first law,

m=Z×Q
when Q = 96500 coulomb, ‘m’ becomes gram equivalent mass ‘E’.

 E = Z × 96500

EIt
 m=
96500
If ‘Z1’ and ‘Z2’ are the electrochemical equivalents of two substances ‘A’ and ‘B’ and ‘E1’ and ‘E2’ are the
gram equivalent masses of substances ‘A’ and ‘B’ respectively then,
E1 E2
Z1 = and Z2 =
96500 96500
E1 Z1
 =
E 2 Z2

THICKNESS OF COATED LAYER

Let the dimensions of metal sheet to be coated be (a cm × b cm).

Thickness of coated layer = ‘c’ cm
 Volume of coated layer = (a × b × c) cm3
Mass of the deposited substance = Volume × Density
= (a × b × c) × d g

 EIt
(a×b×c)×d=
96500

Sometimes radius of atom of deposited metal is given instead of density, in which case density of the deposited
metal is calculated as,

Radius of silver atom = 10-8 cm

Atomic mass of Ag = 108

Page 8 of 69
 108
Mass of single silver atom = g
6.023 1023
4 3
πr
Volume of single atom =
3
= 4/3 × 3.14 × (10-8)3 cm3
108
 6.023 10
Mass of single atom 23
Density of Ag = = 42.82 g cm-3
Volume of single atom 4
 3.14  (108 )3
3
FARADAY’S SECOND LAW

According to Faraday’s Second Law,

“When the same quantity of charge is passed through different electrolytes, then the masses of different
substances deposited at the respective electrodes will be in the ratio of their equivalent masses.”

The law can be illustrated by passing same quantity of electric current through three voltmeters containing
solutions of H2SO4, CuSO4 and AgNO3 respectively as shown below.
In the first voltmeter, hydrogen and oxygen will be liberated, in the second, copper will be deposited and in the
third, silver will be deposited.

Mass of hydrogen Equivalent mass of hydrogen

=
Mass of copper Equivalent mass of copper
Mass of copper Equivalent mass of copper
=
Mass of silver Equivalent mass of silver
Mass of silver Equivalent mass of silver
=
Mass of hydrogen Equivalent mass of hydrogen

It is observed that by passing one coulomb of electric charge,

Hydrogen evolved = 0.00001036 g
Copper deposited = 0.0003292 g
Silver deposited = 0.001118 g

These masses are in the ratio of their equivalent masses.

From these masses, the amount of electric charge required depositing one equivalent of hydrogen or copper or
silver can be calculated.
1
For hydrogen =  96500 coulomb
0.00001036

Page 9 of 69
 31.78
For copper =  96500 coulomb
0.0003292
107.88
For silver =  96500 coulomb
0.001118
This follows that 96500 coulomb of electric charge will deposit 1 g equivalent of any substance.

CURRENT EFFICIENCY

Sometimes the ammeter shows false current due to mechanical fault. In this case,

Actualcurrent
Current efficiency = × 100
Ammeter current

SOLVED EXAMPLES (JEE MAIN & JEE ADV.)

Example 1. Chromium metal can be plated out from acidic solution containing CrO3 according to the following
equation: CrO3 + 6H+ + 6e-   Cr(s) + 3H2O. Calculate the mass of chromium that will be plated out by
1200 C of charge.
Solution:
In the reaction: CrO3 + 6H+ + 6e   Cr(s) + 3H2O
1 mol of Cr will be deposited by 6 mol of electrons, i.e. 52 g chromium will be deposited by 6 × 96500 C
charge. Thus, mass of chromium deposited by 1200 C charge
52 1200
=
696500
= 0.1077 g
Example 2. Calculate the mass of copper deposited when a current of 0.3 ampere is passed in aqueous solution
of copper sulphate for two hours.
Solution:
Atomic mass
Equivalent mass of copper =
Valency
63.5
= = 31.75
2
EIt
w=
96500
Given i= 0.3 amp, t = 2 × 3600 sec, E = 31.75 g/eq
Putting these values in the above eqn., we get
0.3  2  3600  31.75
w=
96500
= 0.7106 g

Example 3. Find the charge in coulomb on 1 g-ion of N3-.

Solution:
Charge on one N3- ion = 3×1.6 × 10-19 coulomb
1 g–ion= 6.02 × 1023 ions
 Charge on 1 g-ion of N3-= 3×1.6×10-19×6.02×1023
= 2.89×105 coulomb

Example 4. How many hours does it take to reduce 3 mole Fe3+ to Fe2+ with 2 ampere current?
[Given: F = 96500 coulomb].
Solution:
Page 10 of 69
The required reaction is: Fe3+ + e- 
 Fe2+
3+
i.e. 3 mole Fe will require 3 mole electrons.

∴ Required charge = 3 × 96500 coulomb

= 289500 coulombs
Charge = current × time
 289500 = 2 × t
289500
t = = 1.44750 × 105 sec
2
≈ 40 hr

Example 5. How much electric charge is required to:

(i) Deposit 7.25 g Al from molten Al2O3?
(ii) Reduce 1 mol Cr2O72- into Cr3+?
Solution: (i) Equivalent mass of aluminium in molten Al2O3
Atomic mass 27
= = =9
Valency 3
9 g aluminium will be deposited by 96500 C charge
∴ 7.25 g aluminium will be deposited by
96500
= × 7.25 g coulomb
9
= 77736.1 coulombs

(ii) Cr2O72- + 14H+ + 6e-   2Cr3+ + 7H2O

Reduction of 1 mol Cr2O7 requires 6 mol e-,
2-

i.e. 6 × 96500 C charge

= 579000 coulombs

Example 6. Exactly 0.4 faraday electric charge is passed through three electrolytic cells is series, first
containing AgNO3, second CuSO4 and third FeCl3 solution. How many grams of each metal will be deposited
assuming only cathodic reaction in each cell?
Solution:
The cathodic reactions in the cells are respectively,
Ag+ + e-   Ag
1 mole 1 mole
108 g 1F
Cu2+
+ 2e-   Cu
1 mole 2 mole
63.5g 2F
And Fe3+ + 3e-   Fe
1 mole 3 mole
56 g 3F
Hence, Ag deposited = 108 × 0.4 = 43.2 g
63.5
Cu deposited = ×0.4 = 12.7 g
2
56
Fe deposited = ×0.4 = 7.47 g
3

Example 7. An electric current of 100 ampere is passes through a molten liquid of sodium chloride for 5 hours.
Calculate the volume of chlorine gas liberated at the electrode at NTP.

Page 11 of 69
Solution:
The reaction taking place at anode is: 2Cl-   Cl2 + 2e-
71.0g 71.0 g 2×96500 coulomb
Q = i × t = 100 × 5 × 60 × 60 coulomb
The number of moles of chlorine liberated by passing 100 × 5 × 60×60 coulomb of electric charge
1
= × 100 ×5 × 60 × 60 = 9.3264 mole
2  96500
Volume of Cl2 liberated at NTP = 9.3264 × 22.4 = 208.91 L

Example 8. A 100 watt, 110 volt incandescent lamp is connected in series with an electrolytic cell containing
cadmium sulphate solution. What mass of cadmium will be deposited by the current flowing for 10 hours?
Solution:
Watt = ampere × volt
 100 = ampere × 110
100
 Ampere =
110
Quantity of charge = ampere × second
100
 = ×10× 60 × 60 coulomb
110

The cathodic reaction is: Cd2+ + 2e  Cd

112.4 g 2×96500 C
100
Mass of cadmium deposited by passing ×10×60×60 coulomb charge
110
112.4 100
= × ×10×60×60 = 19.0598 g
2  96500 110

Example 9. In an electrolysis experiment, a current was passed for 5 hours through two cells connected in
series. The first cell contains a solution of gold salt and the second cell contains copper sulphate solution. 9.85 g
of gold was deposited in the first cell. If the oxidation number of gold is +3, find the amount of copper
deposited on the cathode in the second cell. Also, calculate the magnitude of the current in ampere.
Solution:
Mass of Au deposited Eq.mass of Au deposited
Applying the formula, =
Mass of Cu deposited Eq.mass of Cu deposited
197 63.5
Eq. mass of Au = , Eq. mass of Cu =
3 2
63.5 3
 Mass of copper deposited = 9.85 × × g = 4.7625 g
2 197
Let Z be the electrochemical equivalent of Cu.
 E = Z × 96500
E 63.5
 Z= =
96500 2  96500
Applying m = Z × I × t

Given: t= 5 hours = 5 × 3600 second

63.5
 4.7625 = × I× 5 × 3600
2  96500
4.7635296500
I= = 0.804 amperes
63.553600

Page 12 of 69
Example 10. How long has a current of 3 ampere to be applied through a solution of silver nitrate to coat a
metal surface of 80 cm2with 0.005 mm thick layer? [Given: Density of silver is 10.5 g cm-3].
Solution:
Mass of silver to be deposited = volume × density
= Area × thickness × density

Given: Area = 80 cm2, thickness = 0.0005 cm and density = 10.5 g cm-3

Mass of silver to be deposited = 80 × 0.0005 × 10.5 = 0.42 g
Applying to silver E = Z × 96500
108
 Z= g
96500
Let the current be passed for t seconds.
We know that, W = Z ×I× t
108
 0.42 = ×3× t
96500
0.42  96500
 t= = 125.09 seconds
108  3

Example 11. What current strength in ampere will be required to liberate 10g of chlorine from sodium
chloride solution in one hour?
Solution:
Applying the formula, E = Z × 96500 (E for chlorine = 35.5),
35.5
Z= g
96500
Now, applying the formula
m = Z ×I× t
35.5
Where, m = 10 g, Z= , t = 60 × 60 = 3600 seconds
96500
10  96500
 I= = 7.55 amperes
35.5  3600

Example 12. 0.2964 g of copper was deposited on passage of a current of 0.5, ampere for 30 minutes through a
solution of copper sulphate. Calculate the atomic mass of copper.
(1 Faraday = 96500 coulombs)
Solution:
Quantity of charge passed= 0.5 × 30 × 60 = 900 coulombs
The mass of copper deposited by 900 coulombs of charge= 0.2964 g
0.2964
 The mass of copper deposited by 96500 coulombs of charge = × 96500 = 31.78 g
900
Thus, 31.78 is the equivalent mass of copper.

At. Mass = Eq. mass × Valency

 At. Mass= 31.78 × 2 = 63.56

Example 13. Calculate the quantity of electricity that would be required to reduce 12.3 g of nitrobenzene to
aniline if the current efficiency for the process is 50%. If the potential drop across the cell is 3 volts, how much
energy will be consumed?
Solution:
The equation of reduction is: C6H5NO2 + 6H+ + 6e-   C6H5NH2 + 3H2O
∵ 123 g nitrobenzene require 6 × 96500 C, i.e. 579000 C charge
∴ 12.3 g nitrobenzene will require 57900 C charge.
Page 13 of 69
Actual required charge = 2 × 57900
= 115800 C
Efficiency of the current = 50%
Energy consumed = Charge × potential
= 115800 × 3
 = 347400 J

Example 14. Silver is electro deposited on a metallic vessel of total surface are 900 cm2 by using a current of
0.5 amp for 2 hrs. Calculate the thickness of silver deposited. Density of silver = 10.5 g cm-3.
(Atomic mass of silver = 108 amu, 1F = 96500 C)
Solution:
EIt
Mass of deposited silver, m=
96500
0.52 3600108
= = 4.029 g
96500
Mass of silver = Volume × density = Area × thickness × density
4.029 = 900 × x × 10.5
 x = 4.26×10-4 cm

PROBLEMS FOR PRACTICE (JEE MAIN & JEE ADV.)

1. What is the current strength in ampere required to deposit 1.27 g of Cu from a solution of CuSO4 in
1.5 hrs? Ans. 0.71 amp
2. When a current of 0.75 amp is passed through CuSO4 solution of 25 min, 0.369 g of copper is deposited
at the cathode. Calculate the atomic mass of copper. Ans.63.3 amu
3. In the electrolysis of acidulated water, it is desired to obtain hydrogen at the rate of 1 cc per second at
NTP. What should be the current passed? Ans. 8.616 amp
4. How many coulombs are required to produce:
(i) 20 g of calcium from molten CaCl2?
(ii) 50 g aluminium from molten Al2O3? Ans. (i) 96500C (ii) 536111C
5. The electrolysis of a molten salt solution was carried out by passing a current of 4 amp for 45 minutes.
It resulted in deposition of 2.977 g of metal. If atomic mass of metal is 106.4 amu, calculate the valency
of metal ion. Ans. 4
6. How many coulombs of electricity are required for:
(i) Oxidation of 90 g of water?
(ii) Reduction of MnO4– ions in 500 ml of 0.5 M solution Mn2+ions? Ans. (i) 9.65×105C (ii) 120625C
7. How many grams of chlorine can be produced by the electrolysis of molten NaCl by a current of
1 ampere for 15 minutes? Ans. 0.333 g Cl2

CONDUCTANCE AND CONDUCTORS

“Substances which allow the passage of electric current through them are called conductors.”

Electrical conductors are two types:

➢ Metallic conductors or Electronic conductors.

➢ Electrolytic conductors.

METALLIC (or) ELECTRONIC CONDUCTORS

“Conductors which transfer electric current by transfer of electrons, without transfer of any matter, are
known as metallic or electronic conductors.”
Page 14 of 69
These materials contain electrons which are relatively free to move.
The passage of current through these materials has no observable effect other than a rise in their temperature.

For example, Metals such as copper, silver, aluminium, etc., nonmetals like carbon (graphite—an allotropic
form of carbon) and various alloys belong to this class.

ELECTROLYTIC CONDUCTORS

“Conductors in which the flow of electric current is not by virtue of flow of electrons as in metallic
conductors but as a result of movement of charged particles called ions towards the respective oppositely
charged electrodes are known as electrolytic conductors.”
For example, Aqueous solutions of acids, bases and salts belong to this class.

The passage of current through electrolytic conductors is accompanied by chemical decomposition

The ions which carry positive charge and move towards cathode are termed as cations while ions carrying
negative charge which move towards anode are called anions.
When these ions reach the boundary between a metallic and an electrolytic conductor, electrons are being either
attached to or removed from the ions.
Removal of electrons is termed oxidation (de-electronation) which occurs at anode while addition of electrons
is called reduction (electronation) that takes place at cathode.
In order to pass the current through an electrolytic conductor (aqueous solution or fused electrolyte), two rods
or plates (metallic conductors) are always needed which are connected with the terminals of a battery. These
rods or plates are known as electrodes.
The electrode through which the current enters the electrolytic solution is called the anode (positive
electrode) while the electrode through which the current leaves the electrolytic solution is known as cathode
(negative electrode).

DISTINCTION BETWEEN METALLIC AND ELECTROLYTIC CONDUCTION

S.No. Metallic conduction Electrolytic conduction
1. Electric current flows by movement of Electric current flows by movement of ions.
electrons.
2. It does not involve the transfer of any It involves transfer of matter in the form of ions.
matter.
3. No chemical change occurs. Ions are oxidized or reduced at the electrodes.
4. Resistance increases with increase of Resistance decreases with increase of
temperature. temperature.
5. Faraday law is not followed. Faraday law is followed.

ELECTROLYTIC CONDUCTANCE
Conductance is the property of the conductor (metallic as well as electrolytic) which facilitates the flow of
electricity through it.

“Conductance is equal to the reciprocal of resistance.”

1 1
 Conductance = =
Resistance R

The unit of conductance is ohm-1 or mho or siemens.

Page 15 of 69
SPECIFIC CONDUCTANCE (or) CONDUCTIVITY

The resistance of any conductor varies directly to its length (l) and inversely to its cross-sectional area (a).

l
 Rα
a
l
 R= ρ
a
where,
 - the specific resistance or resistivity.

If l= 1 cm and a = 1 cm2,
 R=𝜌

“The specific resistance or resistivity is thus, defined as the resistance of one centimeter cube of a conductor.”

“The reciprocal of specific resistance is termed as the specific conductance or conductivity.”

or
“Specific conductance or conductivity is defined as the conductance of one centimeter cube of an electrolytic
solution.”

In the case of electrolytic solutions,

“The specific conductance is defined as the conductance of a solution of a definite dilution enclosed in a
cell having two electrodes of 1cm2 cross section area are separated by one centimeter apart.”

Note:
When an electrolytic solution is diluted its specific conductance decreases because number of ions, i.e.
current carriers present per unit volume decreases.

Specific conductance or conductivity is denoted by the symbol kappa ( к ).

1
 к=
ρ

where,
к = kappa - the specific conductance, ρ - the specific resistance or resistivity
a
 ρ = .R
l

where,
l 1
- Cell constant, =G - Conductance
a R

 Specific conductance = Conductance × Cell constant

Unit of specific conductance = ohm-1 cm-1 or siemens cm-1

Specific conductance of Specific conductance Specific conductance

= +
an electrolytic solution of an electrolyte of solvent
i.e κ Electrolytic solution = κ Electrolyte +κSolvent

Page 16 of 69
When two solutions of same electrolyte having different specific conductance or conductivity are mixed, then
specific conductance of resultant solution may be calculated as,
к1V1 + к 2 V2 = к R  V1 +V2 
where,
κ1 , κ 2 - specific conductances of the two solutions which are mixed.
κ R - resultant specific conductance.
V1, V2 - the volume of electrolytic solutions, which are mixed.

EQUIVALENT CONDUCTANCE ( Λeq )

“Equivalent conductance is defined as the conductance of all the ions produced by one gram equivalent of
an electrolyte in a given solution.”
Consider a rectangular trough with two opposite sides made of metallic conductor (acting as electrodes) exactly
1 cm apart. If cm3 (1 ml) solution containing 1 gram equivalent of an electrolyte is placed in this container and
conductance is measured.

According to definitions,
Conductance = Specific conductance ( κ ) = Equivalent conductance ( Λeq )
If the solution is diluted to say (1000 cm3 or 1000 ml), the conductance of the solution will be 1000 times the
specific conductance. But even now, the measured conductance is equal to the equivalent conductance because
the solution still has 1 g equivalent of the electrolyte.

 Equivalent conductance, Λeq  1000  κ

In general, Λeq = κ x V
where,
‘V’ is the volume in ml containing 1 g equivalent of the electrolyte.

In case, if the concentration of the solution is ‘C’ g equivalent per litre (1000cm3), then the volume containing 1g
equivalent of the electrolyte will be 1000/C.
1000
 Λeq = κ x
C
1000
 Λeq = κ x
N

where,
‘N’- Normality

The unit of equivalent conductance is ohm-1 cm2 equiv-1.

MOLAR CONDUCTANCE ( Λm )

“The molar conductance of an electrolytic solution is defined as the conductance of all the ions produced by
ionization of 1 g mole of an electrolyte.”

Mathematically, it may be defined as, m  k x V

where,
‘V’ - volume of an electrolytic solution containing 1 g mole of electrolyte
Page 17 of 69
Let molarity of solution be ‘M’
1000
 V=
M
1000
is the volume of the solution containing 1g mole of electrolyte.
M
1000
 Λm =κ x
M

The units of molar conductance are: S m2 mol-1 (or) S cm2 mol-1

Note:
1 S m2 mol-1 = 104 S cm2 mol-1

RELATION BETWEEN MOLAR AND EQUIVALENT CONDUCTANCE

1000
We know that, Λm =κ 
M
1000
CO32- = κ 
N
where,
m and Λeq - molar and equivalent conductance, κ - specific conductance or conductivity of solution.

Dividing both the equations, we get

Λm N
= =Valency factor
Λeq M

 Λm M= Λeq N

SOLVED EXAMPLES (JEE MAIN & JEE ADV.)

Example 15. Electrolytic conductivity of 0.3 M solution of KCl at 298 K is 3.72 × 10-2 S cm-1. Calculate its
molar conductivity.
Solution:
1000
Applying the formula, Λm =κ ×
M
1000
 m = 3.72 × 10-2 ×
0.3
2 -1
=124 Scm mol

Example 16. The measured resistance of a conductivity cell containing 7.5 × 10-3 M solution of KCl at 25℃
was 1000 ohm. Calculate: (i) Specific conductance (ii) Molar conductance of the solution.
[Given: Cell constant = 1.25 cm-1].
Solution:
1
(i) Specific conductance, κ= × Cell constant
R
1
= 1.25
1000
= 1.243 × 10-3 ohm-1 cm-1

Page 18 of 69
 1000
(ii) Molar conductance Λm =κ ×
M
1000
= 1.243 × 10-3 ×
7.5 10-3
= 165.73 ohm-1 cm2 mol-1

Example 17. A 0.05 N solution of a salt occupying a volume between two platinum electrodes separated by a
distance of 1.72 cm and having an area of 4.5cm2 has a resistance of 250 ohm. Calculate the equivalent
conductance of the solution.
Solution:
Applying the formula, Specific conductance = Conductance x Cell constant
l
 κ=C×
a
1 l
= ×
R a
1 1.72
= 
250 4.5
= 1.5288 × 10-3 ohm-1 cm-1
1000
 Λeq = κ ×
N
1000
= 1.5288 x 103×
0.05
= 30.56 ohm cm2 eq-1
-1

Example 18. Resistance of a solution (A) is 50 ohm and that of solution (B) is 100 ohm, both solutions (A) and
(B) are mixed, what will be the resistance of the mixture, using the same cell? Assume that there is no increase
in the degree of dissociation of (A) and (B) on mixing.
Solution:
Let us suppose 1 and  2 are the specific conductance of solution ‘A’ and ‘B’ respectively and cell constant is
‘y’.
Applying the formula, Specific conductance = Conductance x Cell constant
1
For (A), κ1 = ×y
50
1
For (B), κ2 = ×y
100
When equal volumes of (A) and (B) are mixed, the volume becomes double. Then,
κ +κ
Specific conductance of mixture = 1 2
2
κ1 + κ 2 1
 = ×y
2 R
1y y  1
 + = ×y
2  50 100  R
1 1 1
 + =
100 200 R
= 200/3
= 66.66 ohm

Page 19 of 69
Example 19. Specific conductance of a decinormal solution of KCl is 0.0112 ohm-1 cm-1. The resistance of a
cell containing the solution was found to be 56 ohms. What is the cell constant?
Solution:
Applying the formula, Specific conductance = Cell constant × Conductance
Specific conductance
 Cell constant =
Conductance
= Specific conductance × Resistance
= 0.0112 × 56
= 0.6272 cm-1

Example 20. The specific conductivity of 0.02 M KCl solution at 25 0 C is 2.768 x 10-3 ohm-1 cm-1.
The resistance of this solution at 25 0 C when measured with a particular cell was 250.2 ohm. The resistance of
0.01M CuSO4 solution at 25 0 C measured with the same cell was 8331 ohm. Calculate the molar conductivity of
the copper sulphate solution.
Solution:
Specific conductivity of KCl
Cell constant =
Conductance of KCl
2.768103
=
1/ 250.2
= 2.768 x 10-3 × 250.2
For 0.01 M CuSO4 solution,
Specific conductivity = Cell constant x Conductance
1
= 2.768 x 10-3 × 250.2 ×
8331
1000
Molar conductance = Specific conductivity ×
C
3
2.76810 250.2 1000
= 
8331 1/100
= 8.312 ohm-1 cm2 mol-1

Example 21. 1.0N solution of a salt surrounding two platinum electrodes 2.1 cm apart and 4.2 sq cm in area
was found to offer a resistance of 50 ohm. Calculate the equivalent conductivity of the solution.
Solution:
Given, l =2.1 cm, a = 4.2 sq cm, R = 50 ohm
l 1
Specific conductance, κ = ×
a R
2.1 1
 κ=  = 0.01 ohm-1 cm-1
4.2 50
Equivalent conductivity = κ  V
where, V = the volume containing 1 g equivalent = 1000 ml

 Equivalent conductivity = 0.01  1000 = 10 ohm-1 cm2 equiv-1

Example 22. The conductivity of a solution containing 1 gram of anhydrous BaCl2 in 200 cm3 of water has
been found to be 0.0058 mho cm-1. What are the molar conductivity and equivalent conductivity of the
solution? (Atomic mass of Ba = 137, Atomic mass of chlorine = 35.5.)
Solution:
w ×1000
Molarity of BaCl2 solution can be calculated as, M = B
MB ×V

Page 20 of 69
 11000
 M= = 0.024
208200
1000
Λm =κ  .
M
1000
 m = 0.0058 
0.024
= 241.67 ohm-1 cm2 mol-1
Molar conductivity
Equivalent conductivity =
Valencyfactor
241.67
 Λeq = = 120.83 ohm-1 cm2 eq-1
2

Example 23. The resistance of 0.5 M CH3COOH solution is 100 ohm. The cell constant is 0.035 cm-1.
Calculate molar conductivity of solution.
Solution:
l 1
Applying the formula, specific conductance, κ= ×
A R
l
Given: Cell constant   = 0.035 cm-1, R=100 ohm
a
1
Putting these values in the above equation, we get, κ = 0.035 
100
= 3.5  10 ohm-1 cm-1
-4

1000
Molar conductance of solution may be calculated as, Λm =κ ×
M
1000
= (3.5 × 10-4) × = 0.7 ohm-1 cm2 mol-1
0.5

PROBLEMS FOR PRACTICE (JEE MAIN & JEE ADV.)

8. A 0.01M solution of KCl has specific conductance 0.0014 ohm-1 cm-1. A cell filled with this solution
has a resistance of 4.2156 ohm. What is the cell constant? Ans. 0.00594 cm-1
9. The conductivity of an aqueous solution of sodium chloride in a cell is 92 x 10-4 ohm-1 cm-1.
The resistance offered by the cell is 247.8 ohm. Calculate the cell constant for the cell. Ans. 2.28 cm-1
10. The resistance of 0.01 M solution of an electrolyte is 100 ohm at 298K.
Calculate (i) Conductance (ii) Conductivity (iii) Resistivity. The cell constant of the cell is 1 cm-1.
Ans. (i) 10-2 ohm-1 (ii) 10-2 ohm-1 cm-1 (iii) 100 ohm cm
11. The conductivity of 0.2 M solution of KCl at 289K is 0.0248 S cm-1. Calculate its molar conductivity.
Ans. 124 ohm-1 cm2 mol-1
12. If conductivity of N/50 KCl solution at 298 K is 0.002765 ohm-1 cm-1 and resistance of a cell containing
this solution is 100 ohm, calculate the cell constant. Ans. 0.2765 cm-1
13. 0.5M solution of a salt placed between the platinum electrodes 2 cm apart and each of area of cross-
section 4 cm2 has a resistance of 25 ohm. Calculate the value of Λm of the solution.
Ans. 40 ohm-1 cm2 mol-1

Page 21 of 69
FACTORS AFFECTING CONDUCTANCE (MOLAR (or) EQUIVALENT)
Since electrolytic conduction depends on the mobility of ions, anything that inhibits the motion of ions causes
resistance to current flow.
There are a number of factors that influence the conductance of an electrolytic solution, viz. interionic
attraction, solvation of ions, viscosity of solution, number and speed of ions, and temperature.

TEMPERATURE

The average kinetic energy of ions increases as the temperature is increased and therefore, the resistance of
electrolytic conductors’ decreases (i.e. conduction increases) as the temperature is raised.

NATURE OF ELECTROLYTE

Conductance depends on the number of ions.

A solution which contains larger number of ions compared to another solution of the same concentration at
same temperature has more conducting power and is said to be a stronger electrolyte.
The fraction of total molecules present in solution as ions is known as degree of ionization or degree of
dissociation.
Number of molecules dissociated into ions
α=
Total number of molecules

Note:
It has been observed that all electrolytes do not ionize to the same extent. Some are almost completely ionized
while others are feebly ionized.

FACTORS AFFECTING THE DEGREE OF IONIZATION OF AN ELECTROLYTE IN SOLUTION

NATURE SOLVENT

The main function of the solvent is to weaken the electrostatic forces of attraction between the two ions and
separate them and any solvent which has high value of dielectric constant has the capacity of separating ions.

Note:
Water is considered to be the best solvent as it has the highest dielectric constant.

NATURE OF SOLUTE

When the ionizable parts of a molecule of a substance are held more by covalent bonding than by electrovalent
bonding, less ions are furnished in solution, and such substances are termed weak electrolytes.
Strong electrolytes are almost completely ionized in solution.

For example,
Weak electrolytes: H2S, HCN, NH4OH, CH3COOH etc…
Strong electrolytes: NaCl, Ba(NO3)2, KOH, etc.

TEMPERATURE

The degree of ionization increases with the increases of temperature, because at higher temperature molecular
speed is increased which overcomes the forces of attraction between the ions.

Page 22 of 69
DILUTION

The extent of ionization of an electrolyte is inversely proportional to the concentration of its solution.
Thus, degree of ionization increases with the increases of dilution of the solution, i.e. decreasing the
concentration of the solution.

The effect of dilution on the degree of dissociation of a weak electrolyte is given by Ostwald’s dilution law.

OSTWALD’S DILUTION LAW

Weak electrolytes are not completely ionized when dissolved in a polar medium like water, and hence there
exists equilibrium between ions and unionized molecules
AB A+ +B-
Applying the concept of the law of mass action for the above ionic equilibrium, we get
A+  B-  Cα ×Cα
K=    =
 AB C(1- α)
Cα 2
 K= . . . (i)
1- α
For weak electrolytes, α is very small,  (1-α) 1
 K=Cα2

K
 α= . . . (ii)
C

At constant temperature, since ‘K’ remains constant,

1
 α α
C
 C 
 0, α 
1 .
It can thus be understood that, as dilution increases or as concentration decreases, the degree of ionization ‘𝜶′
of a weak electrolyte increases.
As the degree of ionization increases both equivalent and molar conductance increases.

VARIATION OF MOLAR CONDUCTANCE (or) EQUIVALENT CONDUCTANCE WITH

CONCENTRATION

Let us examine the values of Λeq for some electrolytes at different concentrations as given in the graph below:

Experiment observations show that both molar and equivalent conductivity of solution increases on dilution.
The variation is however different for strong and weak electrolytes.
Page 23 of 69
Strong electrolytes have high value of conductance even at normal concentration and there is no rapid increase
in the conductance on dilution, but there is a tendency for molar conductance to approach a limiting value when
the concentration approaches zero. This stage is called infinite dilution.

The equivalent and molar conductance has a limiting value at infinite dilution and is represented by Λ0m and Λ0eq
or  m and Λeq .

Weak electrolytes have low value of molar and equivalent conductance at high concentration but there is a rapid
increase in the value of molar and equivalent conductance with dilution.

There is no indication that a limiting value of equivalent conductance can be attained even when the
concentration approaches zero. Thus, graphically, Λ0m or Λ0eq of weak electrolytes cannot be obtained.

It is thus, concluded that molar and equivalent conductance of electrolytes whether strong or weak increases
with dilution and reaches to a maximum or limiting value which is termed as molar and equivalent
conductance at infinite dilution.

Λ0m and Λ0eq or m and Λeq can be obtained in the case of strong electrolytes by extrapolation of the graph
of molar or equivalent conductance to zero concentration, but in case of weak electrolytes it cannot be
obtained accurately.

THEORY OF STRONG ELECTROLYTES (DEBYE-HUCKEL-ONSAGER THEORY)

Strong electrolytes are completely ionized in the solution. The variation of molar conductivity of a dilute
solution of strong electrolyte on dilution is explained on the basis of Debye-Huckel-Onsager theory.

According to this theory, each ion in the solution is symmetrically surrounded by oppositely charged ions, so
that, the resultant force on the ion is zero. However, when potential difference is applied, the ions move towards
oppositely charged electrodes and as a result the symmetrical ionic atmosphere is distorted which results in a
decrease in speed of the ions.

Debye-Huckel showed that these effects are due to two factors namely:

➢ Asymmetric effect.
➢ Electrophoresis effect.

Page 24 of 69
ASYMMETRIC EFFECT

In presence of external electric field ions move towards oppositely charged electrode. It results into the
distortion of spherical symmetry consequently, the moving ion is pulled back by oppositely charged ions, thus
decreasing the speed of the ion.

ELECTROPHORESIS EFFECT

Ions in the solution are generally solvated and when these ions move, they carry with them the associated
solvent molecules.
Ions do not move in stationary medium, but the molecules of the medium travel in opposite direction to the
movement of ions. This counter-current makes it more difficult for the ion to move through the solution and
thus, slow down its speed.

On dilution both these factors are reduced and speed of ions increases as a result of which conductance of
the solution also increases.

Debye-Huckel and onsager gave the following relation between molar or equivalent conductance with
concentration:
Λ= Λ0 -A C . . . (i)
where
A=constant, which depends on the type of electrolyte, i.e. NaCl (1:1), CaCl2 (1:2), AlCl3 (1:3) type etc.

Note:
All electrolytes of a particular type have same value of A.
The above equation represents the equation of a straight line not passing through origin.
Slope of the line=A, y-Intercept=  0

An indirect method for obtaining Λ0m and Λ0eq for weak electrolytes has been given by Kohlrausch.

Page 25 of 69
KOHLRAUSCH’S LAW OF INDEPENDENT IONIC MIGRATION
“Kohlrausch’s law states that at infinite dilution, where dissociation for all electrolytes is complete
(including weak electrolytes since, α  1 as C   0 ) and where all interionic effects disappear (because
of larger distance between ions), each ion migrates independently and contributes a definite quantity to the
total molar conductivity irrespective of the other ion with which it is associated.”

 Λ0m AB = λ0A+ + λ0B-

Let us consider a general electrolyte Ax By.

A x By 
 xA y+ +yBx-
 Λ0m A B  = xλ0Ay+ + yλ0Bx-
x y

According to Kohlrausch’s law, we should have,

Λ0AB - Λ0CB = λ 0A+ + λ 0B- - λ0C+ - λ 0B-
= λ 0A+ - λ C0 +
and Λ0AB - Λ0AC = λ0A+ + λ 0B- - λ 0A+ - λ 0C-
= λ 0B- - λ 0C-

i.e. the difference between molar conductivities at infinite dilution ( Λ0m ) of electrolytes containing common
ion should be equal to the difference in molar conductivities of ions not in common.

APPLICATION OF KOHLRAUSCH’S LAW

CALCULATION OF ABSOLUTE IONIC MOBILITIES

It has been experimentally found that ionic conductance is directly proportional to ionic mobilities.
λ0+ α u +
λ0- α u -

 λ 0+ =Fu +
 λ0- =Fu -
where,
F=Faraday =96500 coulombs
u+ and u- - ionic mobilities of cations and anions.

Ionic velocity
Ionic mobility =
Potential gradient
Ionic velocity (cm/sec)
Ionic mobility =
Potential difference(volt)/electrode separation

MOLAR CONDUCTANCE OF WEAK ELECTROLYTE AT INFINITE DILUTION

As discussed earlier, the equivalent and molar conductance of weak electrolytes at infinite dilution cannot be
obtained graphically by extrapolation. However, the application of Kohlrausch’s law enables indirect
evaluations in such cases.

Page 26 of 69
For example, molar conductance at infinite dilution of acetic acid can be calculated from equivalent
conductances at infinite dilution of hydrochloric acid, sodium chloride and sodium acetate as illustrated
below:

 
λ 0CH COO- + λ 0H+ = λ 0H+ + λ 0Cl- + (λ 0CH COO- + λ 0Na+ )-(λ 0Na+ + λ 0Cl- )
3 3

 Λ0m(CH3COOH) =Λ0m (HCl) +Λ0m (CH3COONa) -Λ0m (NaCl)

CALCULATION OF DEGREE OF DISSOCIATION (𝜶) OF A WEAK ELECTROLYTE

The values of molar conductance and equivalent conductance at infinite dilution can be used to calculate the
degree of dissociation (𝛼) and also the dissociation constants of weak acids and weak bases.
ΛCm ΛCeq
α= or α=
Λ0m Λ0eq
where,
ΛCm , ΛCeq - Molar and equivalent conductance at concentration ‘C’.
Λ0m , Λeq
0
= Molar and equivalent conductance at infinite dilution.

Knowing the degree of dissociation ‘𝛼’ the dissociation constant ‘K’ of a weak electrolyte can be calculated by
using the relation:
Cα 2
K=
1- α

PROBLEMS FOR PRACTICE (JEE MAIN & JEE ADV.)

Examples 24. The equivalent conductivity of N/10 solution of acetic acid at 25℃ is 14.3 ohm-1 cm2 eq-1.
Calculate the degree of dissociation of CH3COOH if Λ0eq(CH3COOH) is 390.71.
Solution:
ΛCeq 14.3
Degree of dissociation α= =
Λ0eq 390.71
= 0.0366, i.e. 3.66% dissociated

Example 25. Calculate molar conductivity of solution of MgCl2 at infinite dilution from the given data:
λ0Mg2+ = 107.12 ohm-1 cm2 mol-1 and λ0CI- = 76.37 ohm-1 cm2 mol-1
Solution:
MgCl2 
 Mg 2+ + 2Cl-
Λ0MgCl2 = λ0Mg2+ + 2 λ0Cl-
= 107.21 + 2  76.37
= 259.95 ohm-1 cm2 mol-1

Example 26. A decinormal solution of NaCl has specific conductance equal to 0.0092 ohm-1cm-1.
If ionic conductance of Na+ and Cl- ions at the same temperature are 43.0 and 65.0 ohm-1 cm2eq-1 respectively,
calculate the degree of dissociation of NaCl in solution.
Solution: Equivalent conductance of N/10 NaCl solution
Λeq = Sp. Conductivity  Dilution
= 0.0092  10,000
= 92 ohm-1 cm2eq-1
Page 27 of 69
 Λ0eq = λ0Na + + λ Cl
0
-

= 43.0 + 65.0
= 108 ohm-1 cm2eq-1
ΛCeq 92
Degree of dissociation α= 0 = =0.85
Λeq 108
Example 27. At 18℃, the molar conductances at infinite dilution of NH4Cl, NaOH and NaCl are 129.8, 217.4,
108.9 ohm-1 cm2mol-1 respectively. If the molar conductance of N/100 solution of NH4OH is
9.93 ohm-1cm2mol-1, calculate the degree of dissociation of NH4OH at this dilution and also calculate its
dissociation constant.
Solution: Λ0m (NH4Cl) = λ NH+ + λCI- =129.8 . .(i)
4

Λ 0
m (NaOH) = λ Na + + λ OH- =217.4 . .(ii)
Λ0m (NaCl) = λ Na + + λ CI- =108.9 . .(iii)
Adding eqn. (i) and (ii) and subtracting eqn. (iii), we get
λ0NH+ + λ0Cl- + λ0Na + + λ0OH- - λ0Na + - λ0Cl-
4

 λ 0
NH+4
+ λ0OH- = 129.8 + 217.4 – 108.9
Λ0m (NH4OH) = 238.3 ohm-1cm2mol-1
ΛCm 9.93
Degree of dissociation, α= 0 = =0.04167 ,
Λm 238.3
i.e. 4.17% dissociated.
Ammonium hydroxide undergoes dissociation as:
NH4OH (aq) NH+4 +OH-
C 0 0
C-Cα Cα Cα
 NH4  OH  Cα ×Cα Cα 2
+ -

K= = =
 NH4OH C-Cα 1- α
0.01 × (0.04167)2
= = 1.8 × 10-5
1-0.04167

PROBLEMS FOR PRACTICE (JEE MAIN & JEE ADV.)

14. The conductivity of saturated solution of AgCl is 1.24 × 10-6 ohm-1 cm-1. The ionic conductivities of Ag+
and Cl- ions at infinite dilution are 53.8 and 65.3 ohm-1 cm2 mol-1. Calculate the solubility of AgCl in
gL-1 [Given: Molar mass of AgCl= 143.5]. Ans. 1.49 × 10-3 g L-1
15. Calculate the molar conductivity at infinite dilution of AgCl from following data:
Λ0m (AgNO3 ) =133.4, Λ0m (KCl) =149.9, Λ0m (KNO3 ) =144.9 S cm2 mol-1 Ans. 138.45 Scm2mol-1
16. The molar conductivity at infinite dilution of Al2 (SO4)3 is 858 S cm2 mol-1. Calculate the molar ionic
conductivity of Al3+ ion, given that λ 0(SO2- ) is 160 Scm2mol-1. Ans. 189 Scm2mol-1
4

17. The conductivity of 0.001M acetic acid is 4.9x10-5 Scm-1. Calculate its dissociation constant.
[Given: Λ0m (CH3COOH) is 390.5 Scm2mol-1. Ans. 1.85 × 10-5

Page 28 of 69
ELECTRODE POTENTIAL
When a metal is placed in a solution of its ions, the metal acquires either a positive or negative charge with
respect to the solution. On account of this, a definite potential difference is developed between the metal and
the solution.
“The potential difference developed between the metal and the metal ions in solution is called Electrode
potential.”
For example, when a plate of zinc is placed in a solution having Zn2+ ions, it becomes negatively charged
with respect to solution and thus, a potential difference is set up between zinc plate and the solution, called
the electrode potential of zinc.
Similarly, when copper is placed in a solution having Cu2+ ions, it becomes positively charged with respect to
solution. A potential difference is set up between the copper plate and the solution, called electrode potential
of copper.
The potential difference is established due to the formation of electrical double layer at the interface of metal
and the solution.

The development of negative charge (as on zinc plate) or positive charge (as on copper plate) can be explained
in the following manner.

When a metal rod is dipped in its solution, two changes occur:

OXIDATION

Metal ions pass from the electrode into solution leaving electrons and thus, a negative charge on the electrode.
Conversion of metal atoms into metal ions is by the attractive force of polar water molecules.
n+
M(s) M(aq) + ne-
The metal ions go into the solution and the electrons remain on the metal making it negatively charged.
“The tendency of the metal to change into ions is known as electrolytic solution pressure.”

REDUCTION

Metal ions in solution gain electrons from the electrode and start depositing on the metal surface leaving a
positive charge on the electrode.
n+
M(aq) + ne- M(s)
Page 29 of 69
“The tendency of ions in solution to get deposited on the metal surface is termed osmotic pressure.”

In the beginning, both these changes occur with different speeds but soon equilibrium is established.

If electrolytic solution pressure is greater than osmotic pressure, the metal acquires a negative charge with
respect to solution.
If the osmotic pressure is greater than electrolytic solution pressure, the metal acquires positive charge with
respect to solution.

Note:
In practice, one effect is greater than the other and in both the cases a potential difference is set up.
The magnitude of electrode potential of a metal is a measure of its relative tendency to lose or gain electrons,
i.e. it is a measure of the relative tendency to undergo oxidation (loss of electrons) or reduction (gain of
electrons).

The magnitude of potential depends on the following factors:

➢ Nature of the electrode.

➢ Concentration of the ions in solution.
➢ Temperature.

Depending on the nature of the metal electrode to lose or gain electrons, the electrode potential may be of
two types:

OXIDATION POTENTIAL

When electrode is negatively charged with respect to solution, i.e. it acts as anode and oxidation occurs.
n+
M(s) M(aq) + ne-

REDUCTION POTENTIAL

When electrode is positively charged with respect to solution, i.e. it acts as cathode and reduction occurs.
n+
M(aq) + ne- M(s)

STANDARD ELECTRODE POTENTIAL

“The potential difference developed between metal electrode and the solution of its ions of unit molarity
(1M) at 25oC (298 K) is called standard electrode potential.”

Note:
According to the IUPAC convention, the electrode potential is regarded as the reduction potential, i.e. the
given value of electrode potential be regarded as reduction potential unless it is specifically mentioned that it
is oxidation potential.
Reduction potential of an electrode means that reduction reaction is taking place at the electrode, if the
reaction is reversed and written as oxidation reaction, the numerical value of electrode potential will to be
reversed.

i.e., Standard reduction potential = - (Standard oxidation potential)

or
Standard oxidation potential = - (Standard reduction potential)

Page 30 of 69
It is not possible to measure the absolute value of the single electrode potential directly.
Only the difference in potential between two electrodes can be measured experimentally and it is, therefore,
necessary to couple the electrode with another electrode whose potential is known. This electrode is termed as
reference electrode. Knowing the value of electrode potential of the reference electrode, the electrode potential
value of the other electrode can be determined.

REFERENCE ELECTRODE: STANDARD HYDROGEN ELECTRODE (SHE)

SHE consists of a small platinum strip coated with platinum black as to adsorb hydrogen gas.
A platinum wire is welded to the platinum strip and sealed in a glass tube as to make contact with the outer
circuit.
The platinum strip and glass tube is surrounded by an outer glass tube which has an inlet for hydrogen gas at the
top and a number of holes at the base for the escape of excess of hydrogen gas.
The platinum strip is placed in an acid solution which has H+ ion concentration 1M. Pure hydrogen gas is
circulated at one atmospheric pressure.
A part of the gas is adsorbed and the rest escapes through the holes. This gives equilibrium between the
adsorbed hydrogen and hydrogen ions in the solution.
H2 2H+ + 2e-
The temperature of the cell is maintained at 25oC.

The standard hydrogen electrode is arbitrarily assigned a potential of exactly ± 0.000 Volt.
The hydrogen electrode thus, obtained forms one of two half cells of a voltaic cell. When this half-cell is
connected with any other half cell, a voltaic cell is constituted.
The hydrogen electrode can act as cathode or anode with respect to other electrode and hence is referred to
as reversible hydrogen electrode.

Page 31 of 69
 SHE Half Reaction Electrode potential
Anode: H2 2H+ + 2e- 0.0 V
Cathode: 2H+ + 2e- H2 0.0 V

ELECTROCHEMICAL SERIES
By measuring the potentials of various electrodes versus a standard hydrogen electrode (SHE), a series of
standard electrode potentials has been established.
“The series obtained when the electrodes (metals and non-metals) in contact with their ions are arranged on
the basis of the values of their standard reduction potentials or standard oxidation potentials, is called the
electrochemical or activity series of the elements.”
By international convention, the standard potentials of electrodes are tabulated for reduction half reactions,
indicating the tendencies of the electrodes to behave as cathodes towards SHE.

Note:
Those with positive E0 values for reduction half reaction do in fact act as cathode versus SHE, while those
with negative E0 values of reduction half reactions behave instead as anode versus SHE.

STANDARD ELECTRODE POTENTIALS AT 25°C ‘THE ELECTROCHEMICAL SERIES’

Element Electrode Reaction (Reduction) Standard Electrode (Reduction)
potential E°, Volts
Li Li + e 
+ -
 Li -3.05
K K + e 
+ -
K -2.925
Ca Ca + 2e 
2+ -
 Ca -2.87
Na Na + e 
+ -
 Na -2.714
Mg Mg + 2e 
2+ -
 Mg -2.37
Al Al + 3e 
3+ -
 Al -1.66
Zn Zn + 2e 
2+ -
 Zn -0.7628
Cr Cr + 3e 
3+ -
 Cr -0.74
Fe Fe + 2e 
2+ -
 Fe -0.44
Cd Cd2+ + 2e-   Cd -0.403
Ni Ni + 2e 
2+ -
 Ni -0.25
Sn Sn + 2e 
2+ -
 Sn -0.14
H2 2H + 2e 
+ -
 H2 0.00
Cu Cu + 2e 
2+ -
 Cu +0.337
I2 I2 + 2e 
-
 2I- +0.535
Ag Ag + e 
+ -
 Ag +0.799
Hg Hg + 2e 
2+ -
 Hg +0.885
Br2 Br2 + 2e 
-
 2Br - +1.08
Cl2 Cl2 + 2e -
 2Cl - +1.36
Au Au3+ + 3e-   Au +1.50
F2 F2 + 2e 
-
 2F - +2.87

Page 32 of 69
APPLICATIONS OF ELECTROCHEMICAL SERIES

REACTIVITY OF METALS

The activity of metals depends on its tendency to lose electron or electrons, i.e. tendency to form cation (Mn+),
and this tendency depends on the magnitude of standard reduction potential.
The metal which has high negative value or smaller positive value of standard reduction potential readily loses
the electron or electrons and is converted into cation.
The chemical reactivity of metals decreases from top to bottom in the series. The metal higher in the series is
more active than the metal lower in the series.
For example,
Alkali metals and alkaline earth metals having high negative values of standard reduction potentials are
chemically active. These react with cold water and evolve hydrogen.
On the otherhand, metals like Fe, Pb, Sn, Ni, Co, etc, which lie a little down in the series do not react with
cold water but react with steam to evolve hydrogen.
Metals like Cu, Ag and Au which lie below hydrogen are less reactive and do not evolve hydrogen from water.

ELECTROPOSITIVE CHARACTER OF METALS

The electropositive character also depends on the tendency to lose electron or electrons.
Like reactivity, the electropositive character of metals decreases from top to bottom in the electrochemical
series.

On the basis of standard reduction potential values, metals are divided into three groups:

Strongly electropositive metals: Metals having standard reduction potential near about – 2.0 volt or more
negative like alkali metal, alkaline earth metals are strongly electropositive in nature.

Moderately electropositive metal: Metal having values of reduction potentials between 0.0 and about – 2.0 volt
are moderately electropositive. Al, Zn, Fe, Ni, Co, etc., belong to this group.

Weakly electropositive metal: The metals which are below hydrogen and possess positive values of reduction
potentials are weakly electropositive metal. Cu, Hg, Ag, etc., belong to this group.

DISPLACEMENT REACTIONS

Case 1: To predict whether a given metal will displace another metal, from its salt solution:

A metal higher in the series will displace the metal from its solution which is lower in the series, because a
metal higher in the series has greater tendency to provide electrons to the cations of the metal to be
precipitated.
i.e., a metal having low standard reduction potential will displace the metal from its salt’s solution which has
higher value of standard reduction potential.
Case 2: Displacement of one non-metal from its salt solution by another non-metal:

The non-metal which possesses high positive reduction potential has the tendency to accept electrons readily.
These electrons are provided by the ions of the non-metal having low value of reduction potential.
i.e., a non-metal having high value of standard reduction potential will displace another non-metal from its
salt’s solution with lower value of standard reduction potential.

Thus, Cl2 can displace bromine and iodine from bromides and iodides.
Cl2 + 2KI   2KCl + I2

Page 33 of 69
 2I-   I2 + 2e- (Oxidation)
Cl2 + 2e   2Cl- (Reduction)
Note:
The activity or electronegative character or oxidizing nature of the non-metal increases as the value of
reduction potential increases.

DISPLACEMENT OF HYDROGEN FROM DILUTE ACIDS BY METALS

The metal which can provide electrons to H+ ions present in dilute acids for reduction, evolve hydrogen from
dilute acids.
Mn   Mnn+ + ne- (Oxidation)
2H + 2e 
+ -
 H2 (Reduction)
The metal having negative values of reduction potential possess the property of losing electrons.
Thus, the metals occupying top positions in the electrochemical series readily liberate hydrogen from dilute
acids and on descending in the series tendency to liberate hydrogen gas from dilute acids decreases.
The metals which are below hydrogen in electrochemical series like Cu, Hg, Au, Pt, etc., do not evolve
hydrogen from dilute acids.

REDUCING POWER OF METAL

Reducing nature depends on the tendency of the element to lose electrons. Greater the negative reduction
potential, more is the tendency to lose electron or electrons.
The power of the reducing agent increases as the standard reduction potential becomes more and more
negative.
Reducing nature decrease from top to bottom in the electrochemical series.
Element Na Zn Fe
Reducing potential -2.71 -0.76 -0.44

Reducing nature decreases

Note:
Alkali and alkaline earth metals are strong reducing agents.

OXIDIZING NATURE OF NON-METALS

Oxidizing nature depends on the tendency to accept electron or electrons and hence, i.e., greater the value of
reduction potential, higher is the tendency to accept electron or electrons.
The strength of an oxidizing agent increases as the value of reduction potential becomes more and more
positive. Thus, oxidizing nature increases from top to bottom in the electrochemical series.
Element I2 Br2 Cl2 F2
Reduction potential + 0.53 + 1.06 + 1.36 + 2.85

Oxidising nature increases

 F2 is a stronger oxidant than Cl2, Br2 and I2.
Cl2 is a stronger oxidant than Br2 and I2.

THERMAL STABILITY OF METALLIC OXIDES

The thermal stability of a metal oxide depends on its electropositive nature.

As the electro positivity decreases from top to bottom, the thermal stability of the oxide also decreases from
the top to bottom.
The oxides of metals having high positive reduction potentials are not stable towards heat.

Page 34 of 69
The metals which come below copper from unstable oxides, i.e. these are decomposed on heating.
1
Ag2O Heat
 2Ag + O2
2
2HgO  Heat
 2Hg + O2
BaO 
 Heat
Na 2O    No decomposition
Al2O3 

SOLVED EXAMPLES (JEE MAIN & JEE ADV.)

Example 28: Four metals A, B, C and D have their standard reduction potential value equal to -0.14 volt,
+0.34 volt, -1.66 volt and +0.80 volt respectively. Arrange these metals in the decreasing order of reactivity.
Solution:
The metal which has higher negative value of reduction potential is more reactive. Thus, the reactivity of these
metals will decreases in order of
C > A > B > D
-1.66 -0.14 +0.34 +0.80 Reduction potentials

Decreasing order


Example 29: Iron can displace copper from copper sulphate solution but silver does not displace copper. Why?
Solution:
The position of iron in the electrochemical series is above copper but of silver is below copper. Iron having low
reduction potential is capable of providing electrons to Cu2+ ions for reduction but silver is less active than
copper as its reduction potential is higher than copper.
Fe   Fe2+ +2e (Oxidation)
Cu + 2e- 
2+
 Cu (Reduction)
Silver does not provide electrons to Cu2+ ions.

GALVANIC (or) VOLTAIC CELL

“Galvanic or Voltaic cell is an electrochemical setup in which a redox reaction is used to convert chemical
energy into electrical energy.”

The chemical reaction responsible for production of electricity takes place in two separate compartments, each
compartment consists of a suitable electrolyte solution and a metallic conductor.
The metallic conductor acts as an electrode. The compartment containing the electrode and the solution of the
electrolyte is called a half cell.
When the two compartments are connected by a salt bridge and electrodes are joined by a wire through
galvanometer, the electricity begins to flow.

DANIEL CELL
Daniel cell consists of two half cells, the half-cell on the left contains a zinc metal electrode dipped in ZnSO4
solution and the half-cell on the right consists of copper metal electrode in a solution of CuSO4.
The half-cells are joined by a salt bridge that prevents the mechanical mixing of the solution.

Page 35 of 69
When the zinc and copper electrodes are joined by a wire, the following observations are made:

➢ There is a flow of electric current through the external circuit.

➢ The zinc rod loses its mass while the copper rod gains in mass.
➢ The concentration of ZnSO4 solution increases while the concentration of copper sulphate solution
decreases.
➢ The solutions in both the compartments remain electrically neutral.
➢ During the passage of electric current through external circuit, electrons flow from the zinc electrode to
the copper electrode.
➢ At the zinc electrode, the zinc metal is oxidized to zinc ions which go into the solution.
➢ The electrons released at the electrode travel through the external circuit to the copper electrode where,
they are used in the reduction of Cu2+ ions to metallic copper which is deposited on the electrode.

The two half-cell reactions in Daniel cell can be represented as:

Page 36 of 69
Oxidation half reaction:  Zn 2aq  2e
Zns 
Reduction half reaction: Cu 2 aq  2e 
 Cus
Overall redox reaction: Zns  Cu 2aq 
 Cus  Zn 2aq 

SALT BRIDGE AND ITS SIGNIFICANCE

Salt bridge is usually an inverted U-tube filled with concentrated solution of inert electrolytes.
An inert electrolyte is one whose ions are neither involved in any electrochemical change nor do they react
chemically with the electrolytes in the two half cells. Generally, salts like KCl, KNO3, NH4NO3, etc, are used.
For the preparation of salt bridge, gelatin or agar-agar is dissolved in a hot concentrated aqueous solution of an
inert electrolyte and the solution thus, formed is filled in the U-tube. On cooling the solution sets in the form of
a gel in the U-tube.
The ends of the U-tube are plugged with cotton wool as to minimize diffusion effects.

SIGNIFICANCE/FUNCTIONS OF SALT BRIDGE

Salt bridge connects the solutions of two half cells and completes the cell circuit.
It keeps the solutions in two half cells electrically neutral.
In anodic half-cell, positive ions pass into the solution and there shall be accumulation of extra positive charge
in the solution around the anode which will prevent the flow of electrons from anode. The does not happen
because negative ions are provided by salt bridge.

Similarly, in cathodes half-cell negative ions will accumulate around cathode due to deposition of positive ions
by reduction. To neutralize these negative ions, sufficient numbers of positive ions are provided by salt bridge.
Thus, salt bridge maintains electrical neutrality.

Note:
Salt bridge can be replaced by a porous portion which allows the migration of ions without allowing the
solutions to intermix.

Page 37 of 69
REPRESENTATION OF A GALVANIC CELL

The following universally accepted conventions are followed in representing an electrochemical cell:

The anode (-ve electrode) is written on the left hand side and cathode (+ve electrode) on right hand side.
A vertical line or semicolon (;) indicates a contact between two phases.
The anode of cell is represented by writing metal first and then the metal ion present in the electrolytic
solution. Both are separated by vertical line or a semicolon.
For example,
Zn | Zn2+ or Zn; Zn2+
The cathode of the cell is represented by writing the cation of the electrolyte first and then metal.
Both are separated by a vertical line or semicolon.
For example,
Cu2+ | Cu or Cu2+; Cu
The molar concentration or activity of the solution is written in brackets after the formula of the ion.
For example,
Zn | Zn2+ (1M) or Zn | Zn2+ (0.1M)
The salt bridge which separates the two half cells is indicated by two parallel vertical lines.

The Daniel cell can be represented as:

Zn (s) | ZnSO4( aq ) || CuSO4( aq ) | Cu ( s )
Anode Salt bridge Cathode
Oxidation half-cell Reduction half-cell
or Zn | Zn2+ ||Cu2+ | Cu
or Zn | Zn2+ (1M) || Cu2+ (1M) | Cu

EMF OF A GALVANIC CELL

Every galvanic or voltaic cell is made up of two half-cells, the oxidation half-cell (anode) and the reduction
half cell (cathode). The potentials of these half-cells are always different.
On account of this difference in electrode potentials, electric current moves from the electrode at higher
potential to the electrode at lower potential, i.e. from cathode to anode.
The direction of the flow of electrons is from anode to cathode.
Flow of electrons
i.e Anode Flow of current
Cathode
“The difference in potentials of the two half-cells is known as the EMF of the cell or cell potential.”

The EMF of the cell potential can be calculated from the values of electrode potentials of the two half cells
constituting the cell. The following three methods are in use:

Case 1: When standard oxidation potential of anode and standard reduction potential of cathode is given.
E0cell = Standard oxidation potential of anode + Standard reduction potential of cathode
E0cell = E0ox (anode) + E0red (cathode)

Case 2: When standard reduction potentials of both electrodes are given.

E0cell = Standard reduction potential of cathode - Standard reduction potential of anode
E0cell = E0cathode – E0anode
E0cell = E0right – E0left

Case 3: When standard oxidation potentials of both electrodes are given.

E0cell = Standard oxidation potential of anode - Standard oxidation potential of cathode
E0cell = E0ox (anode) – E0ox (cathode)
Page 38 of 69
MEASUREMENT OF STANDARD ELECTRODE POTENTIAL

The measurement of electrode potential of a given electrode is made by constituting a voltaic cell, i.e. by
connecting it with a standard hydrogen electrode (SHE).
1M solution is used in hydrogen half-cell and the temperature is maintained at 250C.
The reading of the voltmeter gives the electrode potential of the Electrode selected w.r.t the hydrogen electrode.

The standard electrode potential of a metal may be determined as it is the potential difference in volt developed
in a cell consisting of two electrodes.

DETERMINATION OF STANDARD ELECTRODE POTENTIAL OF Zn/Zn2+ ELECTRODE

A Zinc rod is dipped in 1M Zinc nitrate solution and this half-cell is combined with a standard hydrogen
electrode through a salt bridge. Both the electrodes are connected with a voltmeter as shown in the figure
below.

Page 39 of 69
The deflection of the voltmeter indicates that current is following from hydrogen electrode to metal electrode or
the electrons are moving from zinc rod to hydrogen electrode.
The zinc electrode acts as an anode and the hydrogen electrode as cathode and the cell can be represented as:
Zns Zn 2aq Haq H2g 
The cell reactions are:
At Anode At Cathode
Zn Zn 2+ +2e- +
2H + 2e- H2

The EMF of the cell is 0.76 volt

E0cell  E0Anode  E0Cathode
 0.76 = E0Anode + 0
 0
E Anode = + 0.76V

As the reaction on the anode involves the oxidation of Zinc, E0Anode is the standard oxidation potential of Zinc.
i.e E0 Zn/Zn 2+ = 0.76 volt
 Standard reduction potential of Zn, i.e. E0 Zn2+ /Zn = - E0ox = - (+0.76)
= - 0.76 volt

DETERMINATION OF STANDARD ELECTRODE POTENTIAL OF Cu2+/Cu, ELECTRODE

A copper rod is dipped in 1M solution of CuSO4.

It is combined with hydrogen electrode through a salt bridge.
Both the electrodes are joined through a voltmeter.
The deflection of the voltmeter indicates that current is flowing from copper electrode towards hydrogen
electrode, i.e. the electrons are moved from hydrogen electrode to copper electrode.
The hydrogen electrode acts as an anode and the copper electrode as a cathode.
The cell can be represented as: H2 g H aq  Cu 2 aq Cu (s)
The cell reactions are:
At Anode At Cathode
H2 2H+ + 2e- Cu 2+(aq) + 2e- Cu (s)

The EMF of the cell is 0.34 volt.

E0cell  E0Anode  E0Cathode
 0.34  0  E0Cathode
 E0Cathode = + 0.34V

Since, the reaction on the cathode is reduction, i.e.Cu2+ + 2e- 

 Cu, E0 Cathode is the standard reduction
potential of copper.

 E0ox (standard oxidation potential of copper) = -0.34 volt

DIFFERENCE BETWEEN EMF AND POTENTIAL DIFFERENCE

S. No EMF Potential difference
1. It is the potential difference between two It is difference of the electrode potentials of the
electrodes when no current is flowing in the two electrodes when the cell is under operation.
circuit.

Page 40 of 69
 2. It is maximum voltage that the cell can It is always less than the maximum value of
deliver. voltage which the cell can deliver.

3. It is responsible for the steady flow of It is not responsible for the steady flow of current
current in the cell. in the cell.

WORK DONE BY THE CELL

Let ‘n’ faraday charge be taken out of cell of EMF ‘E’ then work done by the cell will be calculated as:
Work = Charge × Potential
= nFE
Work done by the cell is equal to decrease in free energy.
 -ΔG = nFEcell
Similarly, maximum obtained work from the cell will be, wmax = nFE0
 -ΔG0 = nFE0cell

PREDICTION FOR OCCURRENCE OF A REDOX REACTION

Any redox reaction would occur spontaneously only if the free energy change (∆G) is negative.

The free energy change is related to EMF of cell as,

ΔG = -nFEcell

The standard free energy change is related to standard EMF of cell as,
ΔG0 = -nFEcell
0

where,
‘n’– number of electrons involved in the cell reaction.
F –Faraday constant, i.e. 96500 C.
E – EMF of the cell.
E0 – Standard EMF of the cell.

Note:
For the cell reaction to be spontaneous in the given direction, ∆G must be negative, for which EMF of the
cell must be positive.

PROBLEMS FOR PRACTICE (JEE MAIN & JEE ADV.)

18. Which of the following reaction will be feasible?
(i) ZnSO4 + Cu(s)   CuSO4 + Zn(s)
(ii) CuSO4 + Zn(s)   ZnSO4 + Cu(s)
Given: E Zn 2+ /Zn = -0.76 V; E0Cu 2+ /Cu = +0.34V
0

Ans. (ii) Is feasible. Metal with lesser standard reduction potential will displace other
metal from its salt, thus zinc will displace copper from the solution of copper sulphate.
19. Construct a galvanic cell using following electrodes:
E0Zn 2+ /Zn = -0.76V ; E0Cu2+ /Cu = +0.34V. Calculate its standard EMF. Ans. +1.10 volt
20. Construct the cells in which the given reactions are taking place. Which electrode shall act as anode
(negative electrode) and which one as cathode (positive electrode)?
(i) Zn + CuSO4   ZnSO4 + Cu
Page 41 of 69
 (ii) Cu + 2AgNO3   Cu(NO3)2 + 2Ag
(iii) Zn + H2SO4   ZnSO4 + H2
(iv) Fe + SnCl2   FeCl2 + Sn
21. Consider the cell: Zn | Zn2+ (aq) (1.0 M) | | Cu2+ (aq) (1.0M) | Cu
The standard electrode potentials are:
Cu2+ + 2e-   Cu(aq) ; E0 = 0.350 volt
Zn2 + 2e-   Zn(aq) ; E0 = -0.763volt
(i) Write down the cell reaction.
(ii) Calculate the EMF of the cell. Ans. 1.113 volt
2+ 2+
22. Will Fe be oxidized to Fe by reaction with 1.0M HCl? E° for Fe / Fe = +0.44 volt.
Ans. EMF = 0.44 volt. Since, EMF is positive, the reaction shall occur.
23. The value of E° of some of the reactions are given below:
I2 + 2e-   2I- ; E° = +0.54 volt, Cl2 + 2e-   2Cl- ; E° = +1.36 volt
Fe3+ + e-   Fe2+ ; E° = +0.76 volt, Ce4+ + e-   Ce3+ ; E° = +1.60 volt
Sn4+ + 2e-   Sn2+ ; E° = +0.15 volt
On the basis of the above data, answer the following questions.
(i) Whether Fe3+ oxidizes Ce3+ or not?
(ii) Whether I2 displaces chlorine from KCl?
(iii) Whether the reaction between FeCl3 and SnCl2 occurs or not?
Ans. Fe3+ does not oxidize Ce3+, I2 does not displace Cl2 from KCl, Fe3+ will oxidize Sn2+
24. Can we use a copper vessel to store 1M AgNO3 solution? Given that E0Cu 2+ /Cu = 0.34V and E0Ag+ /Ag =
0.80V. Ans. Since, EMF is +ve, copper reacts with AgNO3, hence, AgNO3 solution cannot be
stored in a copper vessel.

NERNST EQUATION
The electrode potential and the EMF of the cell depend upon the nature of the electrode, temperature and
the activities (concentrations) of the ions in solution.

For a general reaction such as,

m 1 A + m2 B + … n1X + n2Y +….. …. ... (1)
occurring in the cell, the Gibbs free energy change is given by the equation,
a nX1 ×a Yn2 …..
∆G = ∆G + 2.303RT log m1 m2
o
…….. (2)
a A ×a B ……

where,
‘a’ - activities of reactants and products under a given set of conditions.
∆Go - free energy change for the reaction when the various reactants and products are present at standard
conditions.

The free energy change of a cell reaction is related to the electrical work that can be obtained from the cell as
Gcell  nFEcell
and Go cell  nFE0cell .
On substituting these values in eq. (2), we get
a nX1 ×a Yn2 …..
-nFE cell = - nFE0 cell + 2.303 RT log …….. (3)
a mA1 ×a mB 2 ……
2.303RT a n1 ×a n2 …..
 E cell = E0cell – log10 mX mY …….. (4)
nF a A1 ×a B 2 ……
Page 42 of 69
This equation is known as Nernst equation.

Putting the values of R = 8.314 JK-1 mol-1, T = 298 K and F = 96500 C, Eq.(4) reduces to
0.0591 a n1 ×a n2 …..
E cell = E0cell – log10 mX mY …….. (5)
n a A1 ×a B 2 ……

Note:
In case of dilute solutions the term activities can be replaced with molar concentrations.

0.0591 [ Products ]
 E cell = E0cell – log10 ……… (6)
n [Reactants]

POTENTIAL OF SINGLE ELECTRODE (ANODE)

Consider the general oxidation reaction,

n+
M(s) M(aq) + ne-
Applying Nernst equation,
0.0591 [ Mn+ ]
E ox = E0ox– log10
n [M ]
where,
Eox - oxidation potential of the electrode (anode), E0ox - standard oxidation potential of the electrode.

The concentration of pure solids and liquids are taken as unity.

0.0591
 Eox = E0ox – log10 [Mn+ ]
n

POTENTIAL OF SINGLE ELECTRODE (CATHODE)

Consider the general reduction reaction,

n+
M(aq) + ne- M(s)
Applying Nernst equation,
0.0591 [ M]
Ered = E0 red – log10
n [ M n+ ]
where,
Ered - reduction potential of the electrode (cathode), E0red - standard reduction potential of the electrode.

The concentration of pure solids and liquids are taken as unity.

0.0591 1
 Ered = E0red – log10
n [M n+ ]

Let us consider a Daniel cell to explain the above equations. The concentrations of the electrolytes are not 1 M.

The reaction taking place in the Daniel cell is: Zn s  Cu 2 a q  Zn 2a q   Cu s 
The cell can be represented as: Zns Zn 2aq Cu 2aq Cu (s)

Page 43 of 69
POTENTIAL OF ZINC ELECTRODE (ANODE)

0.0591
Eox = E0ox – log10 [Zn2+]
n

POTENTIAL OF COPPER ELECTRODE (CATHODE)

0.0591
Ered = E0red + log10 [Cu2+]
n

EMF OF THE CELL

Ecell = Eox + Ered
0.0591 [Zn 2+ ]
 Ecell = (E0ox+ E0red) - log10
n [Cu 2+ ]
0.0591 [Zn 2+ ]
 Ecell = E0cell – log10
n [Cu 2+ ]
The value of n = 2 for both zinc and copper.

Let us consider an example, in which the values of n for the two ions in the two half cells are not same.

For example, in the cell,

Cu | Cu2+ || Ag+ | Ag
The cell reaction is:
Cus  2Ag ( aq ) 
 Cu 2 ( aq )  2Ag(s)
The two half -cell reactions are:
Cu   Cu2+ +2e-……………….(1)
Ag+ + e-  Ag………………...(2)

The second equation is multiplied by 2 to balance the number of electrons.

 2Ag+ + 2e-   2Ag

0.0591
 Eox = E0ox - log10 [Cu2+]
2
0.0591
 E red = E0red + log10 [Ag+]2
2
 Ecell = E ox + E red
0.0591 [ Cu 2+ ]
 Ecell = E0 ox + E0red - log10 2
2  Ag + 
0.0591 [ Cu 2+ ]
 Ecell = E0cell - log10 2
2  Ag + 

CONCEPT OF EQUILIBRIUM IN ELECTROCHEMICAL CELL

In an electrochemical cell a reversible redox process takes place,

For example in Daniel cell:

Zns  Cu 2aq Cus  Zn 2aq 

Page 44 of 69
At equilibrium reaction quotient becomes equal to equilibrium constant, i.e., Q=K e
Oxidation potential of anode = - Reduction potential of cathode

 EMF of the cell = Oxidation potential of anode + Reduction potential of cathode = 0

 At equilibrium, potential of both electrodes become equal and current stop flowing in the circuit.

When EMF of the cell = 0, the cell is fully discharged.

According to Nernst equation at 250C:

0 0.0591
Ecell =Ecell - log10Q
n
At equilibrium, Ecell = 0, Q = K
0.0591
 E0cell = log10 K
n
 nE0cell 
 K= Antilog  
 0.0591 

THE RELATIONSHIP AMONG K, ΔG0 AND E0cell

SOLVED EXAMPLES (JEE MAIN & JEE ADV.)

Example 30. Construct the cells in which the following reactions are taking place. Which of the electrodes shall
act as anode (negative electrode) and which one as cathode (positive electrode)?
(i) Zn + CuSO4   ZnSO4 + Cu
(ii) Cu + 2AgNO3   Cu(NO3)2 + 2Ag

Page 45 of 69
(iii) Zn + H2SO4   ZnSO4 + H2
(iv)Fe + SnCl2   FeCl2 + Sn
Solution:
(i) In this case Zn is oxidized to Zn2+ and thus, acts as anode (negative electrode) while Cu2+ is reduced to
copper and thus acts as cathode (positive electrode). The cell can be represented as,
Zn|ZnSO4 ||CuSO4|Cu (or) Zn|Zn2+ || Cu2+ | Cu
(ii) In this case Cu is oxidized to Cu2+ and Ag+ is reduced to Ag. The cell can be represented as,
Cu |Cu (NO3)2||AgNO3|Ag (or) Cu | Cu2+ ||Ag+|Ag
(iii) In this case Zn is oxidized to Zn2+ and H+ is reduced to H2. The cell can be represented as,
Zn|ZnSO4||H2SO4 |H2 (Pt) (or) Zn| Zn2+|| 2H+|H2 (Pt)
(iv) Here, Fe is oxidized to Fe2+ and Sn2+ is reduced to Sn. The cell can be represented as,
Fe|FeCl2||SnCl2|Sn (or) Fe|Fe2+||Sn2+|Sn

Example 31. Consider the reaction, 2Ag+ + Cd   2Ag + Cd2+

The standard electrode potentials for Ag+   Ag and Cd2+   Cd couples are 0.80 volt and -0.40 volt,
respectively.
(i) What is the standard potential E0 for this reaction?
(ii) For the electrochemical cell in which this reaction takes place which electrode is negative electrode?
Solution:
(i) The cathode half reaction is: 2Ag+ + 2e-   2Ag,
E0Ag + ∕ Ag = 0.80 volt (Reduction potential)

The anode half reaction is: Cd   Cd2+ + 2e- ,

E0Cd2+∕ Cd = - 0.40 volt (Reduction potential)
or E0Cd ∕ Cd2+ = 0.40 volt (Oxidation potential)
0 0 2+ 0 +
E = E Cd ∕ Cd + E Ag Ag = 0.40 + 0.80 = 1.20 volt

(ii) The negative electrode is always the electrode whose reduction potential has smaller value or the electrode
where oxidation occurs. Thus, Cd electrode is the negative electrode.

Example 32. Consider the cell: Zn Zn 2 aq 1.0 M  Cu 2 aq  1.0 M  Cu
The standard electrode potentials are:
Cu 2 aq   2e 
 Cu (s) E0 = 0.350 volt
Zn 2 aq  2e 
 Zn (s) E0 = - 0.763 volt
(i) Write down the cell reaction.
(ii) Calculate the EMF of the cell.
Solution:
(i) Reduction potential of Zn is less then copper, hence, Zn acts as anode and copper as cathode.
At anode: Zn   Zn2+ + 2e- (Oxidation)
At cathode: Cu + 2e 
2+ -
 Cu (Reduction)
2 2
Cell reaction: Zn  Cu   Zn  Cu

(ii) E0cell = E0Zn ∕ Zn2+ + E0Cu2+ ∕ Cu

= Ox. potential Zinc + Red. potential of copper
E0Zn2+ ∕ Zn = - 0.763 (Reduction potential)
0 2+
E Zn ∕ Zn = + 0.763 (Oxidation potential)
And E0Cu2+ ∕ Cu = 0.350 (Reduction potential)
0
So, E cell = 0.763 + 0.350 = 1.113 volt

Page 46 of 69
Example 33. The values of E0 of some of the reaction are given below:
I2 +2e 
 2I- E0 = +0.54 volt
Cl2 +2e 
 2Cl- E0 = +1.36 volt
Fe3+ +e   Fe2+ E0 = +0.76 volt
Ce3+   Ce4+ +e E0 = +1.60 volt
𝑆𝑛4+ + 2𝑒 −   𝑆𝑛2+ E0 = +0.15 volt
On the basis of the above data, answer the following questions:
(i) Whether Fe3+ oxidizes Ce3+ or not?
(ii) Whether I2 displaces chlorine from KCl?
(iii) Whether the reaction between FeCl3 and SnCl2 occurs or not?
Solution:
(i) Chemical reaction, Fe3+ +Ce3+   Fe2+  Ce4+
The two half reactions are,
Fe3+ +e   Fe2+ E0 = 0.76 volt
Ce3+   Ce4+ +e E0 = - 1.60 volt
Adding -0.84 volt
Since, EMF is negative, the reaction does not occur, i,e. Fe3+ does not oxidize Ce3+.

(ii) Chemical reaction, I2 + 2KCl   2Kl + Cl2

The Two half reactions are,
I2 +2e  2I- E0 = 0.54 volt
2Cl- 
 Cl2 +2e E0ox = - 1.36 volt
Adding -0.82 volt
Since, EMF is negative, the reaction does not occur, i,e. I2 does not displace Cl2 from KCl.

(iii) Chemical reaction, SnCl2 + 2FeCl3   SnCl4 + 2FeCl2

The Two half reactions are,
Cl2 +2e   2Cl- E0 = 0.76 volt
Sn 2+ 
Sn 4+ +2e E0 = - 0.15 volt
Adding 0.61 volt
Since, EMF is positive, the reaction will occur.

Example 34. Calculate the electrode potential at a copper electrode dipped in a 0.1 M solution of copper
sulphate at 250 C. The standard electrode potential of Cu2+ / Cu system is 0.34 volt at 298 K.
Solution:
0.0591
We know that, Ered = E0red + log10 [Cu2+]
n
Putting the values of E0 red = 0.34 V, n = 2 and [Cu2+] = 0.1 M
0.0591
E red = 0.34 + log10 [0.1]
2
= 0.34 + 0.02955 × (-1)
= 0.34 – 0.02955 = 0.31045 volt

Example 35. What is the single electrode potential of a half cell for zinc electrode dipping in 0.01 M ZnSO4
solution at 250C? The standard electrode potential of Zn /Zn2+ system is 0.763 volt at 250C.
Solution:
0.0591
We know that, E ox = E0ox - log10 [Zn2+]
n
Page 47 of 69
Putting the value of E0ox = 0.763 V, n = 2 and [Zn2+] = 0.01 M,
0.0591
E ox = 0.763- log10 [0.01]
2
= 0.763 – 0.02955  (-2)
= (0.763 + 0.0591) volt = 0.8221 volt

Example 36. The standard oxidation potential of zinc is 0.76 volt and of silver is – 0.80 volt. Calculate the
EMF of the cell: Zn Zn  NO3 2 (0.25M) AgNO3 (0.1M) Ag at 250 C.
Solution:
The cell reaction is: Zn + 2Ag+ 
 2Ag +Zn2+
Given: E0ox of Zn=0.76 volt
E0red of Ag=0.80 volt
 E0cell = E0ox+ E0red
= 0.76+0.80 =1.56 volt
0.0591 [Products]
 E cell = E0cell - log
n [Reactants]
0.0591 0.25
= E0cell - log
n 0.1×0.1
0.0591
=1.56 - 1.3979
2
= (1.56-0.0413) volt
=1.5187 volt

Example 37. The EMF (E0) of the following cell is:

Ag | Ag+ (1M) || Cu2+ (1M) | Cu ; E0 = -0.46 volt
Zn | Zn2+ (1M) || Cu2+ (1M) Cu ; E0 = +1.10volt
Calculate the EMF of the cell: Zn | Zn2+ (1M) || Ag+ (1M) | Ag
Solution:
Zn|Zn2+ (1M) || Ag+(1M)| Ag
E0cell = E0ox (Zn / Zn2+) + E 0red (Ag+/ Ag)
With the help of the following two cells, the above equation can be obtained.

Ag | Ag+ (1M) || Cu2+ (1M) | Cu E0 = -0.46 volt

 Cu | Cu2+ (1M) || Ag+ (1M) | Ag E0 =+ 0.46 volt
 + 0.46 = E0ox (Cu / Cu2+) + E 0red (Ag+/ Ag) ……. (1)

Zn | Zn2+ (1M) || Cu2+ | Cu, E0 = 1.10 volt

+1.10 = E0ox (Zn / Zn2+) + E 0red (Cu2+/ Cu) .…. (2)
Adding eqs (1) and (2) we get,
+ 1.56 = E0ox (Cu / Cu2+) + E 0red (Ag+/ Ag) + E0ox (Zn / Zn2+) + E 0red (Cu2+/ Cu)
E0ox (Cu / Cu2+) = - E 0red (Cu
2+
/ Cu)

 + 1.56 = E0ox (Zn / Zn2+) + E 0red (Ag+/ Ag)

Thus, the EMF of the: Zn | Zn2+ (1M) || Ag+ (1M) | Ag is + 1.56 volt.

Example 38. Calculate the EMF of the cell: Mgs Mg 2  0.2 M  Ag  103 M Ags  
Given: E0Ag+/ Ag = + 0.8 volt, E0Mg2+/ Mg = - 2.37 volt
What will be the effect on EMF if concentration of Mg2+ ion is decreased to 0.1 M?

Page 48 of 69
Solution:
E0cell = E0cathode – E0anode
= 0.80 – (-2.37) = 3.17 volt
Cell reaction, Mg + 2Ag 
+
 2Ag + Mg 2+

0.0591 [Mg 2+ ]
Ecell = E0cell – log
n [Ag + ]2
0.0591 0.2
= 3.17 – log
2 [1103 ]2
= 3.17 – 0.1566 = 3.0134 volt
when Mg2+ = 0.1 M
0.0591 0.1
E cell = E0cell – log
2 (1103 )2
= (3.17 – 0.1477) volt
= 3.0223 volt

Example 39. To find the standard potential of M3+ / M electrode, the following cell is constituted:
Pt M M3+  0.0018M  | Ag +  0.01M  Ag . The EMF of this cell is found to be 0.42 volt. Calculate the standard
potential of the half reaction : M3+ + 3e- 
 M.
0 +
Given: E Ag / Ag = 0.80 volt.
Solution:
The cell reaction is: M + 3Ag+   3Ag + M3+
0.0591 [M3+ ]
Applying Nernst equation, E cell = E0cell – log
3 [Ag + ]3
0.0591 (0.0018)
 0.42 = E0cell – log
3 (0.01)3
= E0cell – 0.064
E0cell = (0.42 + 0.064) = 0.484 volt
E0 cell = E0cathode – E0anode
E0anode = E0cathode – E0cell = (0.80 – 0.484) = 0.32 volt

Example 40. Calculate cell potential of the following cell: Zn s Zn 2  0.1M  Pb2 1M  Pbs
Given: E0Zn2+/ Zn = - 0.76 V, E0Pb2+/ Pb = +0.12 V
Solution:
E0 cell = E0cathode – E0anode
= 0.12 – (- 0.76)
= + 0.88 V
Cell reactions are:
Zn (s)  Zn2+ + 2e-
Pb2+ + 2e- 
 Pb (s)
(n = 2)
Zn s + Pb2+ Zn 2+ + Pb
 Zn 2+  0.1
Q= = = 0.1
[Pb2+ ] 1

0.059
 E = E0 – log10 Q
n
0.059
= + 0.88 - log10 (0.1)
n
Page 49 of 69
 = + 0.88 + 0.0295
= + 0.9095V

Example 41. Calculate the standard electrode potential of Ni2+/Ni electrode if the cell potential of the cell:
Ni(s)| Ni2+(0.01 M) || Cu(0.1M)|Cu(s) is 0.59 volt
Given: E0Cu 2+ /Cu = 0.34 volt.
Solution:
Cell process may be given as: Nis +Cu 2+(aq) Cu s +Ni 2+(aq)
0 0.0591 [Ni 2+ ]
Ecell = Ecell - log
n [Cu 2+ ]
0.0591 0.01
 0.59 = E0 - log
2 0.1
 E0 = 0.59-0.0295 = 0.5605V
E0cell =E0Cu2+ /Cu - E0Ni2+ /Ni
 0.5605 = 0.34 - E 0Ni2+ /Ni
 E 0Ni2+ /Ni = - 0.5605 + 0.34 = -0.2205 volt

Example 42. A copper-silver cell is setup. The copper ion concentration is 0.1 M. The concentration of silver
ion is not known. The cell potential when measured was 0.422 V. Determine the concentration of silver ion in
the cell. [Given, E0Ag+/ Ag = + 0.80 V, E0Cu2+/ Cu = + 0.34 V].
Solution:
Cu s Cu 2+  0.1 M  Ag +  C M  Ags
E0cell = E0cathode – E0anode
=E0Ag+/ Ag – E0Cu2+/ Cu
= + 0.80 – 0.34
= + 0.46 V
Electrode processes are:
Anode: Cu(s)   Cu2+ (0.1M) + 2e-
Cathode: 2Ag+ (C) +2e-   2Ag(s)
Cell reaction: Cu s +2Ag  C
+
2Cu 2+  0.1 M  + 2Ag (s) , n = 2
[Cu 2+ ] 0.1
Q= = 2
[Ag + ]2 C

Putting the values in Nernst equation:

0.059
E = E0 – log10Q
n
0.059  0.1 
0.422 = 0.46 - log  2 
2  C 
 0.1  0.46  0.422  2
log  2  =
 C  0.059
= 1.288
 0.1 
 C2  = Antilog (1.288)
 
= 19.40

Page 50 of 69
 0.1
 C= = 0.071 M
19.408

Example 43. Two half-reaction of an electrochemical cell are given below:

MnO-4 (aq) + 8H+(aq) + 5e-   Mn2+ (aq) + 4H2O (l) E0 = + 1.51 V
Sn2+ (aq)  Sn4+(aq) +2e- E0 = + 0.15 V
Construct the redox reaction equation from the two half-reactions and calculate the cell potential from standard
potentials and predict if the reaction is reactant or product favored.
Solution:
Reduction 2× [ MnO 4aq  8Haq   5e Mn 2aq   4H2Ol ] E0red = + 1.51 V
Oxidation 5 × [Sn2+ (aq) 
 Sn4+ (aq) + 2e-] E0red = - 0.15 V

Redox process:

2 MnO-4 aq + 5 Sn 2+ aq + 16H+aq  

 2 Mn 2+aq  + 5Sn 4+aq  + 8H2O(l)
E0Redox process = Standard reduction potential of cathode -Standard reduction potential of oxidation
= + 1.51 – (-0.15)
= + 1.66 V
0
Positive value of E shows that the redox process is spontaneous and the formation of product is favored.

Example 44. For the cell reaction: Mg Mg 2 aq Ag  aq Ag

Calculate the equilibrium constant at 250C and maximum work that can be obtained by operating the cell.
Given: E0Mg2+ /Mg = - 2.37 volt and E0Ag+ /Ag = +0.80 volt.
Solution:
E0cell = 0.80 + 2.37=3.17 volt
nE0cell
 log Kc =
0.0591
2  3.17
= =107.2758
0.0591
 Kc =1.89× 10107
G 0 = Maximum work
= nFE0 = 2  96500  3.17
= 611810 J

Example 45. Calculate the standard free energy change for the following chemical reaction:
2Ag aq  Cds 
 2Ags  Cd2 aq
Given: E0Cd2+/ Cd = - 0.40 V, E0Ag+/ Ag = + 0.80 V.
Solution:
E0Cell  E0Reduction – E0Oxidation
= E0Ag+/ Ag – E0Cd2+/ Cd
= + 0.80 – (- 0.40)
= + 1.20 V
Number of electrons involved in overall redox process = 2, i.e. n = 2.
∆G0 = - nFE0
= - 2× 96500 × 1.20 J
= - 231600 J
= - 231.6 kJ
Page 51 of 69
Example 46. The standard EMF E0of Zn-Cu cell is 1.1 volt at 298K. Calculate the equilibrium constant of the
cell reaction.
Solution:
The cell reaction will be: Zns  Cu 2 aq  Zn 2aq   Cus
Given: n=2, E0=1.10V
nE0cell
K=Antilog
0.0591
=1.94×1037

Example 47. Predict if the following reaction is feasible or not?

Cu 2aq  2Ags Cus  2Ag aq
Given: E0Ag+/ Ag = 0.80 V, E0Cu2+/ Cu = +0.34 V
Solution:
E0Cell  E0Reduction – E0Oxidation
= E0Cu2+/ Cu - E0Ag+/ Ag
= + 0.34 – 0.80
= - 0.46 V
Negative value of E0Cell shows that the reaction is not feasible

Example 48. Calculate the cell EMF and ∆G for the cell reaction at 250C for the cell
Zn s Zn 2  0.0004 M  Cd 2  0.2 M  Cds
E0 value at 250C, Zn2+/ Zn = - 0.763 V, Cd2+/ Cd = - 0.403 V,
F = 96500 coulomb, R = 8.314 J K-1 mol-1
Solution:
E0cell = E0Cd2+/ Cd – E0Zn2+/ Zn
= - 0.403 – (-0.763) = + 0.36 V
2+
The cell process is: Zns Zn  aq Cd 2+ aq Cds
0.0591
E = E0 – log10 Q
n
0.0591 0.0004
= + 0.36 – log
2 0.2
0.0591
= + 0.36 – log 2×10-3
2
0.0591
= 0.36 – (-2.6990)
2
= 0.44 V

∆G = -nFE
= - 2× 96500 × 0.44 = - 84920 J (1 CV = 1J)

Example 49. Estimate the minimum potential difference needed to reduce Al2O3 at 5000C. The free energy
2 4
change for the decomposition reaction: Al2O3   Al + O2, is ∆G = + 960 kJ mol-1.
3 3
[Given: F = 96500 coulomb].
Solution:
∆G = - nFE

Page 52 of 69
 ΔG
 E= -
nF
∆G = - 960000 J mol-1, n=4
960000
E=-
4  96500
= - 2.487 V
∴ Minimum potential difference = 2.487 V

Example 50. Calculate the equilibrium constant for the reaction,

 2Ags  Zn 2aq   2OHaq 
Zns  Ag 2Os  H2Ol 
0
When 𝐸𝑐𝑒𝑙𝑙 = 1.11 volt at 298 K.
Solution:
 nE0 
We know, Kc = Antilog  
 0.0591 
 21.11 
= Antilog  
 0.0591 
= 3.65 × 1037

Example 51. A cell contains two hydrogen electrodes. The negative electrode is in contact with a solution of
10-6 M hydrogen ions. The EMF of the cell is 0.118 volt at 250C. Calculate the concentration of hydrogen ions
at the positive electrode.
Solution:
The cell may be represented as: Pt|H2 (1 atm) | H+ (10-6 M) || H+ (CM) |H2 (1 atm) | Pt
0.0591 [H+ ]cathode
2
Ecell = log
2 [10-6 ]2
[H + ]
 0.118= (0.0591) log
10-6
[H + ]cathode 0.118
 log -6
= =2
10 0.0591
[H + ]cathode
 -6
= 102
10
 [H+]cathode = 10-4 M

Example 52. Calculate the EMF of the following concentration cell:

Zn(s) | ZnSO4 (0.001 M) || ZnSO4 (0.01 M) | Zn(s)
Solution:
Since, both electrodes are made of same metal, hence, E0cell =0.0 volt
Electrode process:
Zns   Zn 2  0.001 M   2e
Zn 2+  0.01 M  + 2e- 
 Zn (s)

Zn 2+  0.01 M  Zn 2+ (0.001 M)
0.001
Q= = 0.1, n = 2
0.01
Substituting the values in Nernst equation, we get
0.0591
E = E0 - log10 Q
n
Page 53 of 69
 0.0591
= E0 - log 0.1
2
= 0.0295 volt

PROBLEMS FOR PRACTICE (JEE MAIN & JEE ADV.)

25. Find the value of equilibrium constant from the following data: E0cell = 0.295 V, T = 298 K, n = 2
Ans. 1010
26. The E0 values corresponding to the following two reducing electrode process are: E0Cu  /Cu = + 0.52 V,
E0Cu2 /Cu + = + 0.16 V. Formulate the galvanic cell for their combination. What will be the standard cell
potential for it? Calculate  G0 for the cell reaction. Ans. 0.36V, - 34740 J mol-1
27. Calculate the equilibrium constant for the following reaction at 298 K.
Cu s  Cl2 g  CuCl2
[Given: E0Cu2+/ Cu = + 0.34 V, E0Cl - = + 1.36 V ] Ans. 3.295×1034
2 /Cl

28. Write the cell formulation and calculate the standard cell potential of the galvanic cell in operation of
which the following reaction takes place: 2Crs  3Cd2aq  
 2Cr 3aq  3Cds
Calculate  G0 for the above reaction.
[Given: E0Cr3+/ Cr = - 0.74 V, E0Cd2+/ Cd = - 0.40 V, F = 96500 C mol-1]
Ans. E0 = + 0.34 V; ∆G0 = - 196.86 kJ mol-1
29. Cr2O7 + 14H + 6e 
2- + -
 Cr + 7H2O
3+ 0
; E = + 1.33 V
2I-  I2 + 2e- ; E0 = - 0.54 V
Find out the value of reaction constant and Gibbs free energy charge in the reaction give.
Ans. ∆G0 = - 457.41 kJ mol-1; K = 1.596 × 1080
30. Represent the cell in which following reaction takes place:
Mgs  2Ag   0.0001 M  Mg 2  0.13 M   2Ags
Calculate Ecell if E0cell = + 3.17 V.  
Ans. Mgs Mg 2  0.130 M  Ag  104 M Ags , E = + 2.96 V
31. Write the Nernst equation and calculate the EMF of the following cell at 298K.
Cu(s) | Cu2+ (0.13 M) || Ag+ (10-4M) | Ag(s)
E0Cu2+/ Cu = + 0.34 V, E0Ag+Ag = + 0.80 V Ans. 0.25 V
32. 2 4

Calculate the free energy change for the following cell: Zns Zn 4 10 M Cd  0.2 M  Cds
2

Given: E0Zn2+/ Zn = - 0.76 V; E0Cd2+/ Cd = - 0.40 V Ans. – 84.92 J
33. Given the following cell: Al(s) | Al3+ (0.01 M) || Fe2+ (0.02 M) | Fe(s)
Calculate ∆G and E cell at 298 K when E0Al3+/ Al and E0Fe2+/ Fe are – 1.66 and – 0.44 respectively.
Ans. E = 1.209 V, ∆G = - 700.01 kJ
2
34. Calculate the equilibrium constant for a reaction: Nis  Cu  aq  Cus  Ni 2aq 
Given E0Ni2+/ Ni = 0.25 V, E0Cu2+/ Cu = + 0.34 V Ans. Kc = 1020
35. At what pH of HCl(aq) will hydrogen gas electrode show electrode potential of -0.118V? The pressure of
hydrogen gas at 298K is 1 atm. Ans. pH = 2
36. Cu + 2e 
2+ -
 Cu(s) 0
; E = + 0.34 V
Ag + e 
+ -
 Ag(s) ; E0 = + 0.80 V
(i) Construct a galvanic cell using above data.
(ii) For what concentration of Ag+ ions will the EMF of the cell be zero at 250C, if the concentration
of Cu2+ is 0.001 M? Ans. 5×10-9 M

Page 54 of 69
CONCENTRATION CELLS
“If two electrodes of the same metal are dipped separately into two solutions of the same electrolyte and are
connected with a salt bridge, the whole arrangement is found to act as a galvanic cell and is called as
Concentration cells.”

There are two types of concentration cells:

➢ Electrode Concentration Cells.

➢ Electrolyte Concentration Cells.

ELECTRODE CONCENTRATION CELLS

In these cells, the potential difference is developed between two like electrodes at different concentrations
dipped in the same solution of electrolyte.

The cell is represented as follows:

Pt, H2 (Pressure P1 ) + H2  Pressure P2  ,Pt
H
Anode Cathode
The EMF of the cell is given by the expression:
0.0591 P 
Ecell = log  1  at 250C
2  P2 
The cell reaction will be spontaneous, i.e. Ecell > 0, when P1 > P2.

Note:
For concentration cells, E0cell =0
Case 2: Amalgam cells, where two amalgams of the same metal at two different are immersed in the same
electrolytic solution.

The cell is represented as follows:

Hg  Zn  C1  Zn 2+
Hg  Zn (C2 )
The EMF of the cell is given by the expression:
0.0591 C
Ecell = log 1 at 250C
n C2

ELECTROLYTE CONCENTRATION CELLS

In electrolyte concentration cells, electrodes are identical but these are immersed in solutions of the same
electrolyte of different concentrations.
The source of electrical energy in the cell is the tendency of the electrolyte to diffuse from a solution of
higher concentration to that of lower concentration.
With the passage of time, the two concentrations tend to become equal and so EMF of the cell gradually falls
to zero.

Page 55 of 69
Case 1: Two hydrogen electrodes at same gas pressures but dipped into different solutions having hydrogen
ions having different concentrations.

The cell is represented as follows:

Pt H2 (p atm) HA (C1M) HB(C2M) H 2 (p atm) Pt
Note:
In such cells, HA and HB would represent strong acids, if their Ka’s are not given while they would be weak
acids, if their Ka’s are mentioned.

For the given cell, the reactions occurring are:

At cathode +
: 2HCathode (C2 M) + 2e- 
 H 2(g) (p atm)
At anode : H 2(g) (p atm) 
 2H +Anode (C1M)+2e-
Net cell reaction +
: 2HCathode (C2 M) 
 2H+Anode (C1M)

Note:
The no. of moles of electrons involved in the above cell reaction i.e. n = 2
The net cell reaction is independent of the pressure terms as the pressure of H2 in the two half cells is same.

Applying Nernst equation to the above cell reaction we get,

0.0591 [H+ ]
Ecell =E0H+ (Cathode) H -E0H+ (Anode) H - log + Anode
2 2
1 [H ]Cathode
0.0591 [H+ ]Cathode
 Ecell = log + ( E0cell =0)
1 [H ]Anode

Note:
The net cell reaction feasible spontaneously only when the EMF of the cell is positive, which is possible only
+ +
when [H ]Cathode > [H ]Anode .

Case 2: Two same metal electrodes dipped in their electrolytic solutions having different concentrations.
The cell is represented as follows:
M(s) Mn+  C1M  Mn+  C2 M  M(s)

The EMF of the cell is given by the following expression:

0.0591 C
Ecell = log 2 at 250C
n C1

Note:
For the cell reaction to be spontaneous, C 2 is greater than C1.

Page 56 of 69
 PROBLEMS FOR PRACTICE (JEE MAIN & JEE ADV.)

36. The observed EMF of the cell Pt H 2 (1atm) H + (3×10-4 M) H + (M1 ) H 2 (1atm) Pt is 0.154V. Calculate
the value of M1 and pH of cathodic solution. Ans. M1=0.12, pH =0.917

Page 57 of 69
37. Calculate the EMF of the following cell: H2 (1atm) HCOOH(0.5M) CH3COOH(1M) H2 (1atm) at
250 C . Given: K a (HCOOH) =1.8×10-4 ,K a (CH3COOH) =1.8×10-5 Ans. Ecell = - 0.0204V
38. Calculate EMF of the following cell: Pt,
H2 (1atm) C2 H5COOH(0.15M) NH4OH(0.01M) H2 ,Pt(1atm)
[Given: Ka (C2 H5COOH)=1.4×10-5 ,K b (NH4OH)=1.8×10-5 ] Ans. Ecell = - 0.46V
39. Calculate the EMF of the electrode concentration cell Pt, H2 (p1 ),HCl,H2 (p2 ),Pt at 250C if P1 =600
torr and P2 =400 torr. Ans. Ecell = 5.19 103V
40. Two weak acid solutions HA1 and HA2 each with the same conc. and having pKa values 3 and 5 are
placed in contact with hydrogen electrode (1 atm, 250C ) and are interconnected through a salt bridge.
Find EMF of cell. Ans. Ecell  0.059V
41. The standard reduction potential of Cu 2+ /Cu and Ag + /Ag solution are 0.337 and 0.799 Volts
respectively. Construct a galvanic cell using these electrodes so that its standard EMF is positive.
For what concentration of Ag+ will the EMF of the cell at 250C be zero, if the conc. of Cu 2+ is 0.1M
Ans. [Ag+ ]=4.67×10-9 M

METAL - INSOLUBLE METAL SALT - ANION HALF-CELL

The assembly of this half-cell is made by dipping a rod of silver coated with a paste of saturated AgCl at the
bottom, in a solution of ionic electrolyte like KCl, NaCl or HCl.

Page 58 of 69
 PROBLEMS FOR PRACTICE (JEE MAIN & JEE ADV.)

44. For the galvanic cell: Ag AgCl(s) ,KCl(0.2M) KBr(0.001M),AgBr(s) Ag .

Calculate the EMF generated and assign correct polarity to each electrode for a spontaneous process
after taking an account of cell reaction at 250C .[ Given: Ksp(AgCl) =2.8×10-10 , Ksp (AgBr) =3.3×10-13 ]
Ans. Ecell =-0.037V
45. The EMF of the cell Ag AgCl(s),  0.05M  KCl (0.05M)AgNO3 Ag is 0.788V. Find the solubility
product of AgCl. Ans. Ksp =1.16×10-16 M 2
46. EMF of the cell Cd CdSO4 H 2SO4 (0.01M) H 2 (1atm),Pt is 0.362 volts at 250C . Calculate the solubility
product of CdSO4 . Given: E0Cd2+ /Cd =-0.403V at 250C . Ans. Ksp = 9.764×10-5M 2
47. The standard reduction potential of the Ag + /Ag electrode at 298K is 0.799V. Given that for AgI
Ksp =8.7×10-17 , evaluate the potential of the Ag + /Ag electrode. Ans. EAg+ /Ag =0.325V
48. Estimate the cell potential of a Daniel cell originally having 1.0M Zn 2+ and 1.0M Cu 2+ ,after sufficient
NH3 is added to the cathode compartment to make the NH3 conc. 2.0M.
[Given: E0Zn/Zn 2+ = 0.76V, E0Cu/Cu2+ =-0.34V, Kf [Cu(NH ) 2+ = 1  1012 ]. Ans. [Cu 2+ ]=6.25×10-14 M, Ecell =0.71V
3 4]

49. EMF of the following cell: Pt, H2 H + (pH=X) 1N KCl Hg 2Cl2(s) ,Hg is 0.67V at 298K

Page 59 of 69
 Calculate pH. [Given: E0CI- /Hg Cl =0.28V ]. Ans. pH = 6.6
2 2 /Hg

50. Calculate the stability constant of the complex [Zn(NH3 )4 ]2+ formed by the reaction:
Zn 2+ +4NH3 [Zn(NH3 )4 ]2+
[Given Zn 2+ (aq) +2e- Zn (s) ; E0 = -0.76V , [Zn(NH3 )4 ]2+ +2e- Zn (s) +4NH3 ; E0 =-1.03V ]
Ans. K=1.42×109

RELATION BETWEEN ELECTRICAL ENERGY AND ENTHALPY OF A CELL

REACTION
According to the Gibbs-Helmholtz equation, the change in free energy of the cell reaction at constant pressure
is given by,
ΔG = ΔH - TΔS

 d(ΔG)    d(ΔG)  
 -ΔG = -ΔH - T    -ΔS =  dT  
 dT p   p 

 d(-nFEcell ) 
 nFEcell = -ΔH - T  
 dT p

 dE 
 nFEcell = -ΔH + nFT  cell 
 dT p
where,
 dEcell 
 dT  - Temperature coefficient of EMF of the cell.
 p
Note:
 dEcell 
 dT  gives the variation of Ecell of a cell reaction with temperature.
 p

Case 1:
 dEcell 
When   = 0.
 dT p
 Electrical energy will be equal to the enthalpy of the cell reaction.

Case 2:
 dEcell 
When   > 0, i.e. Ecell increases with the rise in temperature.
 dT p
 Electrical energy will be greater than the enthalpy of the cell reaction. The additional energy will have to
be supplied to the cell from the surroundings, and if that is not possible, the temperature of the cell will
decrease during the cell reaction.

Page 60 of 69
Case 3:
 dEcell 
When   < 0, i.e. Ecell decreases with the rise in temperature.
 dT p
 Electrical energy will be smaller than the enthalpy of the cell reaction. The additional energy will be
released by the cell to the surroundings, and if that is not possible, the temperature of the cell will
increase during the cell reaction.

COMMERCIAL CELLS AND BATTERIES

Galvanic cells or voltaic cells are used as source of electrical energy. These are commonly called as batteries,
but in fact a battery is a combination of two or more cells in series.
Thus, a battery is nothing but a group of galvanic cells where the chemical energy of redox is converted into
electrical energy.

A useful battery should have the following characteristics:

➢ It should be light and compact, so that it can be used as a portable electric generator.
➢ Its voltage should not vary appreciably during its use.
➢ It should be long lasting even when it is not in use.
Commercial cells are of the following two types:

➢ Primary cells
➢ Secondary cells

PRIMARY CELLS
“In primary cell, once the chemicals have been consumed, further reaction is not possible. i.e. it cannot be
regenerated or recharged by reversing the current flow through the cell using an external direct current
source of electrical energy.”
The most common example of this cell is a dry cell.

DRY CELL

Page 61 of 69
The container of the dry cell is made of zinc which also serves as one of the electrodes.
The other electrode is a carbon rod in the centre of the cell.
A moist mixture of ammonium chloride, manganese dioxide, zinc chloride and porous inert filler occupy the
space between the zinc container and the carbon rod.
As the cell operates, the zinc is oxidized to Zn2+

Anode reaction: Zn   Zn2+ + 2e-

The electrons are utilized at carbon rod (cathode) as the ammonium ions are reduced.
Cathode reaction: 2NH+4 +2e-  2NH3 + H2
The overall cell reaction is: Zn + 2NH+4 
 Zn2+ + 2NH3 + H2

Hydrogen is oxidized by MnO2 in the cell.

2MnO2 + H2   2MnO (OH)
Ammonia produced at cathode combines with zinc ions to form complex ion.
Zn2+ + 4NH3  [Zn(NH3)4]2+
EMF produced in a dry cell is 1.6 volt.

BUTTON CELL
The button cells are usually flat in construction and look like a button in shape and hence the name.
Mercuric oxide button cell is the most commonly used button cell.

Cell consists of, zinc as anode and mercuric oxide plus carbon paste as cathode. The electrolyte is a paste of
ZnO and KOH.

The cell process is given below:

Anode reaction: Zn +2OH- 

 ZnOs +H2O + 2e-
(Amalgam)

Cathode reaction: HgOs + H2O+2e- 

 Hgl + 2OH-
Overall Cell reaction: Zn +HgOs 
 ZnOs + Hg l
(Amalgam)

Note:
The potential of this cell is approximately 1.35 volt and it remains constant during its life because overall
reaction does not involve any ion whose concentration can change during the process.
Owing to their small sizes, button cells are used in small electronic devices like hearing aids, electronic
watches etc. These cells are basically primary cells.

SECONDARY CELLS
“The cells in which original reactants are regenerated by passing direct current from external source, i.e. it
can be recharged, are called secondary cells.”
Page 62 of 69
LEAD STORAGE BATTERY

The anode consists of a group of lead plates containing compressed spongy lead, alternating with a group of
lead plates containing lead dioxide, PbO2 which acts as the cathode.
Both the anode and cathode are immersed in a solution of about 38% H2SO4.

During the cell reaction, the spongy lead is oxidized to Pb2+ ions and lead plates acquire a negative charge.

Anode reaction: Pb   Pb2+ + 2e-

2+
Pb ions combine with sulphate ions to from insoluble lead sulphate, PbSO4, which begins to coat lead
electrode.
Pb2+ + SO2-4   PbSO4
The electrons are utilized at PbO2 electrode.
Cathode reaction: PbO2 + 4H+ +2e-   Pb2+ + 2H2O
Pb2+ + SO2-4   PbSO4
Overall cell reaction is: Pb + PbO2 + 4H+ + 2 SO2-4 
 2PbSO4 + 2H2O

EMF produced in a lead storage cell is 2.041 volt.

A battery consisting of six such cells gives voltage of about 12 volt.

Lead storage cell can be represented as: Pb|PbSO4||H2SO4(aq)|PbO2|Pb

Note:
In the discharging process, the materials of each plate are converted to lead sulphate (PbSO4).
In discharging reactions, sulphuric acid is consumed and water is formed. As a result, the specific gravity of
sulphuric acid falls.
When the specific gravity falls below 1.139, recharging of the battery is required.

Page 63 of 69
CHARGING PROCESS

In the process of charging, lead sulphate (PbSO4) at both electrodes is converted back into spongy lead (Pb)
at negative plate and PbO2 at positive plate.
Further, in the charging process, water is consumed and sulphuric acid is produced and as a result the
specific gravity of sulphuric acid rises.
During the recharging process, the battery acts as an electrolytic cell, overall.

The recharging process may be given as,

2PbSO4s  2H2Ol 
Charging
 Pbs  PbO2s  2H2SO4

PROBLEMS FOR PRACTICE (JEE MAIN & JEE ADV.)

51. During the discharge of a lead storage battery, the density of sulphuric fell from 1.294 g/ml to 1.139 g/ml.
Sulphuric acid of density 1.294 g/ml is 39% by weight and of density 1.139 g/ml is 20% by weight. The
battery holds 3.5 litres of acid and the volume of the acid practically remained constant during the
discharge. Calculate the no. of amphere hour for which the battery must have been used. The anode and
cathode reactions are:
Anode: Pb + SO24   PbSO4 +2e-
Cathode: PbO2 + 4H+ + 2SO42- + 2e-   PbSO4 +2H2O Ans. 265.04 ampere hr
52. A lead storage cell discharges which causes the H2SO4 electrolyte to change from a concentration of
34.6% by weight (density 1.261 g/ml at 250C) to one of 27% by weight. The original volume of
electrolyte is one litre. How many faradays have left the anode of battery? Note the water is produced by
the cell reaction as H2SO4 is used up. Overall reaction is: Pb + PbO2 + 2H2SO4   2PbSO4 +2H2O .
Ans. 1.255 faraday

NICKEL-CADMIUM STORAGE CELL

It is a voltaic cell consisting of an anode of cadmium and a cathode of nickel oxide on nickel. The electrolyte
in the cell is aqueous solution of potassium hydroxide.

Electrode processes are given below:

Anode reaction:  Cd  OH 2  2e

Cathode reaction:
Overall cell reaction:
Cds  2OHaq 
NiO2s + 2H2Ol + 2e- 
 Ni(OH)2 + 2OH-
Cds + NiO2s + 2H 2O l 
 Cd(OH)2 + Ni(OH)2

In the recharging of the cell the process is reversed.

Cd  OH 2  Ni  OH 2 
 Cds  NiO2s  2H2Ol
Note:
It is more expensive than the lead storage battery but it is light, therefore, used in calculators, portable power
tools, etc.

Page 64 of 69
FUEL CELL

The cell consists of three compartments separated by a porous electrode.

Hydrogen gas is introduced into one compartment and oxygen gas is fed into another compartment. These
gases then diffuse slowly through the electrodes and react with an electrolyte, present in the central
compartment.
The electrodes are made of porous carbon and the electrolyte is a resin containing concentrated aqueous
sodium hydroxide solution.
Hydrogen is oxidized at anode and oxygen is reduced at cathode.
The overall cell reaction produces water.

The reactions occurring in the H2-O2 fuel cell are:

Anode reaction : H2g  2OHaq 

 2H2Ol  2e × 2
Cathode reaction : O2g  + 2H2Ol + 4e- 
 4OH-aq 
Overall cell reaction: 2H2 g   O2 g  
 2H2O l

Note:
These types of cells are used in space crafts.
Fuel cells are highly efficient and pollution free.

EFFICIENCY OF THE FUEL CELL

Useful work done
Thermodynamic efficiency of the fuel cell = × 100
Heat of combustion
-ΔG 0
 η= ×100
ΔH0

Page 65 of 69
 nFE0
 η= ×100
ΔH0

PROBLEMS FOR PRACTICE (JEE MAIN & JEE ADV.)

53. In a fuel cell, hydrogen and oxygen react to produce electricity. In the process, hydrogen gas is oxidized at
the anode and oxygen is reduced at the cathode. If 67.2 L of H 2 at STP reacts in 15 minutes, what is the
average current produced? If the entire current is used for electro deposition of copper from copper (II)
solution, what mass of copper will be deposited?
Ans. I=643.34Amps, Mass of copper deposited = 190.4g
CORROSION
“The process of withering away of a metal due to attack of the atmospheric gases on the surface of the metal
resulting into the formation of compounds such as sulphates, sulphides, carbonates, etc, is called corrosion.”

Note:
The process of corrosion of iron is called rusting. Rust is chemically the hydrated oxide of iron having the
formula Fe2O3.xH2O.

MECHANISM OF CORROSION-ELECTROCHEMICAL THEORY

Corrosion is a redox process in which metals are oxidized by oxygen in presence of moisture.
The process of rusting can be explained by considering the formation of an electrochemical cell on the surface
of an iron object.

Rusting of iron involves the following steps:

STEP 1:
The water vapors present in contact with iron surface have dissolved CO2 and O2 from air.
H2O l  CO2g  H2CO3l
Thus, the surface of iron is covered with an aqueous solution of carbonic acid, which undergoes dissociation to
a small extent.
H2CO3 2H+ + CO32- (Ionization of carbonic acid)
H2O H+ + OH- (Ionization of water)
STEP 2:
Second step involves oxidation of iron. Oxidation of metal takes place at the point of strain.
For example, a steel nail first corrodes at the tip and head. The tip of the nail acts as anode where iron is
oxidized to ferrous ion.
Anodic process: Fes   Fe2  2e ; E0Fe2+/ Fe = - 0.44 volt …… (i)

Page 66 of 69
STEP 3:
The electrons flow along the nail to the areas containing impurities which act as cathode where oxygen
(dissolved in water) is reduced to hydroxide ions.

Cathodic process: O2 g  2H2O l  4e 

 4OH ; E 0red = 1.23 volt …….(ii)
The process of reduction involves the following two steps: First of all H+ ions are reduced to hydrogen atoms.

H+ + e- 
 [H] ….. . (iii)

These hydrogen atoms combine with oxygen dissolved in water or from air.
4[H] + O2   2H2O …….(iv)
Combining (iii) and (iv), we get
O2 + 4H+ + 4e-   2H2O(l) .…..(v)
 O2 g  2H2O l  4e 
 4OH ……(vi)

Note:
As the concentration of H+ ions is lowered (i.e. pH is raised), the reduction of oxygen becomes less probable
and less favorable.
It is experimentally found that iron does not rust when it is in contact with a solution of pH above 9 or 10.

Adding equations (i) and (vi), we get, the overall reaction of microcells established on the surface of iron.
2Fes  O2g  4Haq  
 2Fe2aq   2H2Ol ; E0cell =1.67volt

STEP 4:
The ferrous ions (Fe2+) formed in the previous step react with dissolved oxygen or oxygen from air to form
ferric oxide (Fe2O3).
4Fe2+ +O2+4H2O   Fe2O3 + 8H+ (aq)
Hydration of ferric oxide gives rust.
Fe2O3 + xH2O   Fe2O3. xH2O

FACTORS AFFECTING CORROSION

STANDARD REDUCTION POTENTIAL OF METAL

Lesser is the standard reduction potential, greater is the tendency of corrosion. In other words, more is reactivity
of metal, greater is the tendency of corrosion.

STRAINS

Corrosion of metals occurs more readily at points of strain, bend, nick and scratches.

IMPURITY PRESENT ON METAL SURFACE

Presence of impurity in metals increases the probability of their corrosion. Pure metals, e.g. pure iron do not
undergo rusting.

POLLUTION

The acidic oxides like CO2, SO2, NO2, etc. present in air act as catalysts for corrosion. It should be noted that if
iron is placed in vacuum, it does not undergo rusting.
Page 67 of 69
PREVENTION OF RUSTING
USING ANTIRUST SOLUTION

Alkaline phosphate and alkaline chromate solutions are the commonly used antirust solutions.
Alkaline phosphates tend to form an insoluble film of iron phosphate on the surface of iron, thereby protecting
it from corrosion.
In addition, the alkaline nature of an antirust solution decreases the availability of H+ ions which facilitate the
oxidation of Fe to Fe2+.

Note:
Antirust solutions are used to prevent rusting of radiators of cars and water coolers.

BARRIER PROTECTION

Barrier protection uses a coating on the metal surface thereby preventing the surface of the metallic object from
coming in contact with the atmosphere.

This can be achieved by the following methods:

➢ Oil paints on the surface of metal prevents its contact with moist air.
➢ By applying grease or oil on the surface of iron tools and other objects, rusting can be prevented.
➢ Nichrome (Ni + Cr) plating on the surface of iron also acts as a barrier between metal and atmosphere.
➢ Bisphenol is an important chemical which can be applied on the surface of the metal to avoid its corrosion.

SACRIFICIAL PROTECTION

Sacrificial protection uses a coating of a more reactive metal than iron on iron surface.

The metal that is being coated loses electrons, i.e. undergoes oxidation in preference to iron and hence, prevents
the rusting of iron. So, as long as the surface of iron is covered with such metals the corrosion of iron is
prevented.

Zinc metal is the most stable metal to cover iron surfaces. “The process of coating the iron surface by zinc is
called galvanization.”

Zinc metal present on the surface of iron forms a thin protective layer of basic zinc carbonate, i.e.
ZnCO3.Zn(OH)2 due to the reaction between Zinc, oxygen, CO2 and moisture in air.

Zn 2  2e 
 Zn s ; E0Zn 2+ /Zn = -0.76 volt
0
Fe2  2e 
 Fes ; E Fe2+ /Fe = -0.44 volt

Since, standard reduction potential of zinc is less than iron, Zinc will undergo oxidation in preference to iron,
hence, iron will not undergo corrosion (oxidation).

Page 68 of 69
ELECTRICAL (or) CATHODIC PROTECTION

If a buried steel pipe is connected to an active metal. i.e. highly electropositive metal, say magnesium, a voltaic
cell is formed, the active metal is the anode and iron becomes the cathode.
Wet soil or moisture forms the electrolyte.

Electrode reactions are:

Anode reaction:  Mg 2aq  2e
Mgs  ; E0Mg2+ /Mg = - 2.347
Cathode reaction: O2 g +2H2O l + 4e- 
 4OH- (aq) ; E 0red = 1.23 V

Overall reaction: 2Mg s + O2g +2H2Ol 

 2Mg2+ + 4 OH- ; E0cell = 3.60 V

The iron pipe acting as the cathode is protected from oxidation.

Magnesium rod is eventually consumed and must be replaced, but this is cheaper than digging up the pipeline.
This method is used to prevent the rusting of submarines and base line of oil refineries.

Page 69 of 69