CHAPTER: 03 ELECTROCHEMISTRY

Electrochemistry is a branch of chemistry which deals with the study of production of

electricity from energy released during spontaneous chemical reactions and the use of
electrical energy to bring about non-spontaneous chemical transformations.
OR
Electrochemistry is a branch of chemistry which deals with the interconversions of
chemical and electrical energies and study of behaviour of electrolytes.

IMPORTANCE OF STUDY OF ELECTROCHEMISTRY:

The subject of electrochemistry is of importance because of its theoretical implications and
practical applications. It is significant to understand the redox reactions, their free energy
changes and equilibrium conditions at the electrodes of electrochemical cells.
 A large number of metals (such as Al and Na) and compounds such as sodium hydroxide,
chlorine, fluorine and many other chemicals are produced by electrochemical methods.
 Batteries and fuel cells convert chemical energy into electrical energy and are used on a
large scale in various instruments and devices.
 The reactions carried out electrochemically can be energy efficient and less polluting.
Therefore, study of electrochemistry is important for creating new
technologies that are ecofriendly. The transmission of sensory signals through cells to
brain and vice versa and communication between the cells are known to have
electrochemical origin. Electrochemistry is therefore, a very vast and interdisciplinary
subject. In this Unit, we will learn only some of its important elementary aspects.

SOME TERMS USED DURING THE STUDY OF ELECTROCHEMISTRY:

1. CONDUCTORS: Substances which allow the passage of electricity through them are
called conductors.
Examples: Metals, solutions of salts, gases under low pressure.

2. INSULATORS: Substances which do not allow the passage of electricity through them
are called Insulators.
Examples: Glass, rubber, alcohol etc.

TYPES OF CONDUCTORS: Conductors of two types namely.

1. METALLIC CONDUCTORS: Substances which conduct electricity by allowing the flow

of electrons through them are called metals. Hence they are also called electronic
conductors.
Examples: All metals (Copper, aluminium…etc.), Graphite, a non-metal also belongs to
this type of conductor.

2. ELECTROLYTIC CONDUCTORS: Substances which allow the passage of electricity

through them either in the molten state or in the dissolved state due to movement of ions
are called electrolytic conductors.
Examples: Sodium chloride solution, hydrochloric acid etc.

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ELECTRICITY: Electricity is the flow of charges like electrons or ions. An electron
carries a charge of 1.602x10-19 C [Coulomb].

COULOMB (C): It is the unit used for measuring the quantity of electricity.

ONE COULOMB: It is that quantity of electricity when one ampere current flows for one
second.
Q=Ixt
Where, Q= quantity of electricity, I = current n amperes, t= time in seconds

Example:
1. If 10 amperes of current flows for 1 minute (60 seconds) then quantity of current flown is
Q=Ixt
= 10 x 60 = 600 ampere-second = 600 Coulombs.

FARADAY (F): It is unit used to express the total charge carried by all the electrons.
ONE FARADAY (F): It is the charge carried by one mole of electrons.

1 Faraday = Total charge on Avagadro number of electrons = charge on one electron

x 6.022 x 1023 electrons = 1.602 x 10-19 x 6.023 x 1023 coulombs = 96,500 Coulombs

Note: When one faraday of electricity flows through a solution of an electrolyte one
gram equivalent mass of a substance is deposited at an electrode.
JOULE (J): Unit of electrical energy is Joule (1) Joule = Coulomb x volts

ELECTROLYTES AND NON-ELECTROLYTES: Water soluble compounds can be classified

as electrolytes and non-electrolytes.
NON ELECTROLYTES: A non-electrolyte is a compound which doesn't conduct electricity
either in molten state or in aqueous state.
ELECTROLYTES: An electrolyte is a compound, which conducts electricity either in aqueous
state or in molten state and is decomposed by the passage of electric current.
DIFFERENCES BETWEEN ELECTROLYTES AND NON-ELECTROLYTES:

Sl. No. ELECTROLYTES NON-ELECTROLYTES

Conduct electricity either in molten Do not conduct electricity either in molten
1.
state or in aqueous solutions. state or in aqueous solutions.
They do not dissociate into ions in
They dissociate into ions in aqueous
2. aqueous solutions. They are present only
solutions.
as molecules in their aqueous solutions.
They undergo electrolysis and give They do not undergo electrolysis on
3.
products, on passing current. passing current.
They are generally electrovalent
Electrolysis:
4. Electrolysis is defined as a processThey
of chemical
are generally
decomposition
covalentofcompounds.
an electrolyte
compounds.
because of the passage of electricity through its molten state or dissolved state.
Examples: NaCl, HCl, Examples: Urea, glucose, ethanol,
5.
H2SO4…etc sucrose….etc
Based on the extent of ionisation or dissociation, electrolytes are of two types namely:

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i. STRONG ELECTROLYTES: Electrolytes that undergo complete ionisation or dissociation
in their aqueous solutions are called as strong electrolytes.
Examples:
a) All mineral acids: HCl, H2SO4, HNO3, HClO4….etc.
b) All alkali bases: KOH, NaOH….etc.
c) All salts: KBr, NaCl, CH3COONa, CH3COONH4….etc.

ii. WEAK ELECTROLYTES: Electrolytes that undergo partial ionisation or dissociation in

their aqueous solutions are called as weak electrolytes.
Examples:
a) All organic acids: HCOOH, CH3COOH….etc.
b) Certain inorganic acids: HCN, H2CO3, H3BO3, H3PO4….etc.
c) Certain bases: NH4OH, Al(OH)3,Ca(OH)2….etc.

DIFFERENCES BETWEEN STRONG ELECTROLYTES AND WEAK ELECTROLYTES:

Sl. No. STRONG ELECTROLYTES WEAK ELECTROLYTES

Undergoes complete ionisation or Undergoes partial ionisation or
1.
dissociation. dissociation.
2. Degree of ionisation (α) is equal to one. Degree of ionisation (α) is less than one.
Degree of ionisation (α) remains almost Degree of ionisation (α) increases with
3.
same. increase in dilution.
4. They show high electrical conductance. They show low electrical conductance.
Their electrical conductance increases to Their electrical conductance increases
5.
a smaller extent with dilution. to a larger extent with dilution.

DEGREE OF IONISATION (α): It is the ratio of number of molecules of electrolyte dissociated

to the total number of molecules of the electrolyte.
Number of molecules of electrolyte ionised
Degree of ionisation( ) =
Total number of molecules of electrolyte

CELL:
It is a device which converts electrical energy to chemical energy and vice versa.
There are two types of cells namely.
1. Electrolytic cell.
2. Electrochemical cell.

DIFFERENCES BETWEEN ELECTROLYTIC CELL AND ELECTROCHEMICAL CELL:

Sl. No. ELECTROLYTIC CELL ELECTROCHEMICAL CELL

The cell the converts electrical energy to The cell which converts chemical energy
1.
chemical energy to electrical energy

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 Electrical energy is supplied to initiate a Electrical energy is produced due to
2.
non spontaneous redox reaction. spontaneous redox reaction.
Both the electrodes are placed in the The two half cells are set up in different
3. same container in the solution of molten containers and are connected through a
/ aqueous electrolyte. salt bridge or a porous partition.
Electrons are supplied through the Electrons are supplied by the species
4. external battery. They enter through getting oxidised. They move from anode
anode and come out through anode. to cathode in the external circuit.
5. Here, Anode= (+)ve and cathode=(-) ve Here, Anode= (-)ve and cathode=(+) ve

ELECTROLYTIC CELL: The cell which converts electrical energy to chemical energy is
called as an electrolytic cell.
A process called as electrolysis is carried in electrolytic cell.

ELECTROLYSIS: The phenomenon of decomposition of a chemical substance

(electrolyte) on passing electric current is called as electrolysis.

PRODUCTS OF ELECTROLYSIS:
FACTORS AFFECTING PRODUCTS OF ELECTROLYSIS: Products of electrolysis depend on
1. The nature of material being electrolysed.
2. The type of electrodes being used.
3. Standard electrode potential (E0) values of the oxidising and reducing species.
4. Relative molar concentration of the oxidising and reducing species.

TYPES OF ELECTRODES: There are two types of electrodes

1) ACTIVE ELECTRODES: Electrodes which participates in the electrode reaction are called
as active electrodes.
Example: copper, silver, zinc…etc.

2) INERT ELECTRODES: Electrodes which do not participate in the electrode reaction and
acts only as source or sink for electrons are called as inert electrodes.
Example: Graphite, platinum, gold…etc.

NOTE:
 The products of electrolysis are different for reactive and inert electrodes for the same
reaction.
 The products of electrolysis depend on the different oxidizing and reducing species
present in the electrolytic cell and their standard electrode potentials.
 According to preferential discharge theory, during electrolysis the reaction with higher
value of E0 (standard electrode potential) is preferred to take place at cathode and at
anode the reaction with lower value of E0 is preferred to take place.
A reaction against preferential discharge theory can take place due to over potential
requirement.

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 Over potential: Some of the electrochemical processes although feasible, are kinetically
so slow that at lower voltages they don’t occur. In such cases some extra potential called
over potential has to be applied for the discharge of that ion.

CASE-1: ELECTROLYSIS OF MOLTEN SODIUM CHLORIDE SOLUTION:

In this case the electrolytic solution contains only one type of anion and cation i.e. Na+ and Cl–
. During the electrolysis the following reactions occur.
Heat + -
NaCl (s) Na (melt) + Cl (melt)
- 1 -
At anode : Cl (melt) /2 Cl 2(g) + e
+ -
At cathode : Na (melt) +e Na(s)
Heat 1
Over all reaction: NaCl (s) Electrolysis Na(s) + /2Cl 2(g)

Products of electrolysis of molten sodium chloride are a solid sodium metal and
chlorine gas.

CASE-2: ELECTROLYSIS OF AQUEOUS SODIUM CHLORIDE SOLUTION (BRINE):

In this case the electrolytic solution contains four different types of ions (two different types of
anions and two different type of cations) i.e. Na+, H+, Cl– and OH– ions. Hence there exists a
competition between them to get discharged at the respective electrode which is decided by
their standard electrode potential values.

PROBABLE REACTIONS:

AT CATHODE:
At the cathode there is competition between the following reduction reactions:
+ - 0
Na (aq) +e Na(s) E (cell) = -2.71V
+ - 1 0
H (aq) +e /2H2(g) E (cell) = 0.00V

During electrolysis the reaction with higher value of E0 is preferred to take place at
cathode, therefore, the reaction is:
+ - 1 0
H (aq) +e / 2H2(g) E (cell) = 0.00V
But H+(aq) is produced by the dissociation of H2O,
+ -
H2O(l) H (aq) + OH (aq)
Therefore, the net reaction at the cathode may be written as the sum of the above two
reactions as follow
- 1 -
H2O (l) + e / 2 H2(g) + OH (aq)

AT ANODE:
At the anode the following oxidation reactions are possible:

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 - 1 - 0
Cl (aq) /2Cl 2(g)+ e E (cell) = 1.36V
+ - 0
2H2O(l) O2(g) + 4H (aq) + 4e E (cell) = 1.23V
The reaction at anode with lower value of E0 is preferred and therefore, water should
get oxidised in preference to Cl–(aq). However, on account of over potential of oxygen,
oxidation of chloride ion is preferred when compared to oxidation of water. Thus, the net
reactions may be summarised as:
H2O + -
NaCl (aq) Na (aq) + Cl (aq)
- 1 -
At anode : Cl (aq) / 2 Cl 2(g) + e
- 1 -
At cathode : H2O(l) + e / 2 H2(g) + OH (aq)
+ - 1 1
Over all reaction: NaCl (aq) + H2O(l) Na (aq) + OH (aq) + / 2H2(g) + / 2Cl 2(g)

Products of electrolysis of aqueous sodium chloride solution are a sodium hydroxide

(caustic soda), hydrogen gas and chlorine gas.

OVER POTENTIAL:
Some electrochemical process though feasible, are kinetically so slow that at lower
voltages they do not occur , in such cases some extra voltage is required to discharge
that ion (more than the theoretical value of standard electrode potential value). This
extra voltage is called over voltage OR bubble voltage.

CASE-3: ELECTROLYSIS OF SULPHURIC ACID:

In this case both dilute sulphuric acid concentrated sulphuric acid contain H2O and H2SO4 but
their relative molar concentrations are different.
In dilute sulphuric acid relative concentration of H2O is more and H2SO4 is less
where as in concentrated sulphuric acid the relative concentration of H2SO4 is more and H2O
is less.
In this case the electrolytic solution contains three different types of ions
(two different types of anions and only one type of cation) i.e. SO42–, OH– and H+, ions. Hence
there exists a competition between them to get discharged at the respective electrode which
is decided by their relative molar concentrations rather than their standard electrode potential
values.

AT CATHODE: Only one type of reaction occurs at cathode for electrolysis of both dilute and
concentrated sulphuric acid. i.e reduction of H+ ions to H2 gas.
+ - 1 0
H (aq) +e / 2H2(g) E (cell) = 0.00V

AT ANODE:
During the electrolysis of sulphuric acid, the following two processes are possible at the anode:

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 + - 0
2H2O(l) O2(g) + 4H (aq) + 4e E (cell) = 1.23V ........(1)
2- 2- - 0
SO4 (aq) S2O8 (aq) + 2e E (cell) = 1.96V ........(2)

For dilute sulphuric acid, reaction (1) is preferred but at higher concentrations of
H2SO4 reaction (2) is preferred.
 Products of electrolysis of dilute sulphuric acid are H2 gas and O2 gas in a ratio of
2:1 by volume.
 Products of electrolysis of concentrated sulphuric acid are H2 gas and persulphate
ion.

Note: Here in these reactions the standard electrode potentials are replaced by electrode
potentials given by Nernst equation to take into account the concentration effects.

QUANTITATIVE ASPECTS OF ELECTROLYSIS:

Michael Faraday was the first scientist who described the quantitative aspects of electrolysis.
After his extensive investigations on electrolysis of solutions and melts of electrolytes, Faraday
published his results during 1833-34 in the form of laws known as Faraday’s laws of
electrolysis:

FARADAY'S FIRST LAW OF ELECTROLYSIS:

The amount of a substance deposited, dissolved or liberated at an electrode is directly
proportional to the quantity of electricity passing through the electrolytic solution
during electrolysis.

Quantitative aspects of the first law,

If w is the mass of the a substance deposited, dissolved or liberated at an electrode by the
passage of Q coulombs of electricity, then according to first law
w α Q ………(1)
But Q =I x t where I is current in amperes and t is the time in seconds during which current
has flown.
From equation (1) we get w α lt or w = ZIt
Where, ‘Z’ is a constant called electrochemical equivalent.

ELECTROCHEMICAL EQUIVALENT (ECE):

It is the mass of a substance deposited on passing one ampere current for one second
through an electrolytic solution.
OR
It is the mass of a substance deposited on passing one coulomb current through an
electrolytic solution.
The unit of electrochemical equivalent is gram per coulomb (gC-1).
96,500 coulombs of current deposits one gram equivalent mass of a substance.
Gram equivalent mass
Electrochemical equivalence (Z)=
96500

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APPLICATIONS OF THE FIRST LAW:
1. Electrochemical equivalent can be calculated.
2. Mass of different substances discharged when a known quantity of electricity flows through
their solutions can be calculated.

EQUIVALENT MASS: It is the number of arts by mass of an element that combines

with or displaces 1.008 parts by mass of H2 or 8 parts by mass of O2 or 35.5 parts by
mass of Cl2.
At. mass Mol. mass
Eq.mass of an Element = Eq.mass of an Salt =
Valency Total charge on the cation
Mol. mass
Eq.mass of an Acid = Basicity = No. of replacable H+ ions
Basicity
Mol. mass
Eq.mass of an Base = Acidity = No. of replacable OH- ions
Acidity
Mol. mass
Eq.mass of an oxidising or reducing agent =
Change in oxdn. No.

Molar Gram equivalent Molar volume Gram equivalent

Element
mass mass @ STP volume@ STP
H2 2g 1g 22.4L 11.2L
O2 32g 8g 22.4L 5.4L
Cl2 71g 35.5g 22.4L 11.2L
Al 27g 9g ------ ------
Cu 63.5g 31.75g ------ ------
Zn 65.4g 32.7g ------ ------
Ag 108g 108g ------ ------

FARADAY'S SECOND LAW OF ELECTROLYSIS:

When same quantity of electricity passes through solutions of different electrolytes the
amounts of substances liberated at the electrodes are directly proportional to their
equivalent masses.
Illustration:
Let W1 and W2 be the masses of substances 1 and 2 discharged at the electrodes when same
quantity of electricity flows. Let E1 and E2 be the equivalent masses respectively.
From the second law we have W1 α E1 and W2 α E2.
W1 E1
Hence, =  WαE
W2 E2

APPLICATIONS OF THE SECOND LAW:

 Equivalent mass of elements can be calculated.
 Quantity of electricity required to discharge a given mass of a substance can be calculated.

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ELECTROCHEMICAL CELLS:

The cells which convert the chemical energy liberated during the spontaneous redox
reactions to electrical energy are called as electro chemical cells or galvanic cells or
voltaic cells.
Example: Daniel cell, Leclanche cell…etc.

CONSTRUCTION OF A GALVANIC CELL AND THEIR REPRESENTATION:

We can construct innumerable number of galvanic cells on the pattern of Daniel cell by taking
combinations of different half-cells.
 Each half cell consists of a metallic electrode dipped into an electrolyte.
 The two half-cells are connected by a metallic wire through a voltmeter and a switch
externally.
 The electrolytes of the two half-cells are connected internally through a salt bridge.
Sometimes, both the electrodes dip in the same electrolyte solution and in such cases we
don’t require a salt bridge.
 In a galvanic cell, the half-cell in which oxidation takes place is called anode and it has a
negative potential with respect to the solution. The other half-cell in which reduction takes
place is called cathode and it has a positive potential with respect to the solution.
 Thus, there exists a potential difference between the two electrodes and as soon as the
switch is in the on position the electrons flow from negative electrode to positive electrode.
 The direction of current flow is opposite to that of electron flow.
 The potential difference between the two electrodes of a galvanic cell is called the cell
potential and is measured in volts.
 The cell potential is the difference between the electrode potentials (reduction potentials)
of the cathode and anode. It is called the cell electromotive force (e.m.f) of the cell when
no current is drawn through the cell.
 It is now an accepted convention that we keep the anode on the left and the cathode on
the right while representing the galvanic cell.
 A galvanic cell is generally represented by putting a vertical line between metal and
electrolyte solution and putting a double vertical line between the two electrolytes
connected by a salt bridge.
 Under this convention the e.m.f of the cell is positive and is given by the potential of the
half-cell on the right hand side minus the potential of the half-cell on the left hand side.
0
Ecell  Ecathode
0
 Eanode
0

ELECTRODE POTENTIAL:
It is the potential developed by the metal with respect to the solution of its own ions
after attainment of equilibrium is called electrode potential.
OR
The potential developed when a metal is in equilibrium with the solution of its own ions
is called electrode potential.

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ORIGIN OF ELECTRODE POTENTIAL- NERNST THEORY:
When a metal rod is dipped in the solution of its own ions, two opposing reactions occur.
a. The metal tends to become metal ions due to oxidation i.e. by loosing electrons.
b. The metal ions in the solution tend to become metal due to reduction i.e. by gaining
electrons.
After some time an equilibrium gets established as given below,
oxidation n+ -
M reduction
M + ne

If this equilibrium lies towards the right side, then the metal acquires positive charge and
attracts around it a layer of negatively charged ions and vice versa. Thus, an electrical double
layer appears. This double layer is the origin for the development of electrode potential.

STANDARD ELECTRODE POTENTIAL:

The potential developed by the metal when it is in equilibrium with one molar solution
of its own ions at 298K is called standard electrode potential.
Note:
 If the electrode contains a gas the pressure should be 1 bar (100 kPa).
 Standard electrode potentials are of two types, namely:
a. Standard reduction potential (SRP): It is the standard electrode potential expressed
for the reduction reaction of the electrode. It is the measure of tendency of the metal
ions to gain electrons.
b. Standard oxidation potential (SOP): It is the standard electrode potential expressed
for the oxidation reaction of the electrode. It is the measure of tendency of the metal
ions to lose electrons.
 SRP and SOP of an electrode have the same magnitude but in opposite signs.

Example:
SRP of zinc electrode= E Zn2+ /Zn  0.76V
0

SOP of zinc electrode = E Zn/Zn2+  0.76V

0

The unit of electrical potential is volt (V)

1Volt: It is defined as 1J of work done per coulomb of electricity (charge) transferred.

NOTE:
According to IUPAC conventions, standard reduction potentials are now called
standard electrode potentials.

FACTORS AFFECTING ELECTRODE POTENTIAL:

1. Nature of the electrode material (metal): Highly electropositive metals like sodium
potassium…etc. they possess a strong tendency to lose electrons (undergo oxidation),
such a metals reduction potential is highly negative (E0 Na= -2.71V). If a metal is less
electropositive or in case of electronegative elements like chlorine, bromine …etc. they

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 possess a strong tendency to gain electrons (undergo reduction), such a metals/ elements
reduction potential is positive.

2. Temperature: As the temperature increases the reduction potential of the electrode

increases.

3. Molar concentration of the solution (metal ions): The quantitative dependence of

electrode potential on the molar concentration of metal ions is given by Nernst equation.

SALT BRIDGE:
It is U- shaped glass tube filled with agar-agar jelly mixed with KCl / KNO3 / NH4NO3.

Note: The salt bridge is prepared using KCl / KNO3 / NH4NO3 only because the mobility of the
anions and cations are same.

FUNCTION OF SALT BRIDGE:

It minimises liquid-liquid junction potential and allows the passage of ions to maintain electrical
neutrality around the electrodes.

SYMBOLIC REPRESENTATION OF ELECTROCHEMICAL CELL:

Let us consider a galvanic cell made up of two half cells A and B. let the oxidation occur
at A and reduction occur at B, thus the galvanic cell is represented as follows,
n+ n+
Al A (conc.) ll B (conc.) l B
A single vertical line in the cell representation represents solid liquid – interface across which
the potential difference exists. The double vertical line represents a salt bridge in a cell.
Electrode where reduction occurs is written on R.H.S of the salt bridge and the
electrode where oxidation occurs is written on L.H.S of the salt bridge.
Hint:
 LOAN= left side oxidation anode negative.
 OIL RIG= oxidation is loss of electrons and reduction is gain of electrons.
 Sign conventions of electrodes in cells.

ELECTROLYTIC CELL GALVANIC CELL

ELECTRODE
Sign Reaction Sign Reaction
ANODE + ve oxidation - ve oxidation
CATHODE - ve Reduction + ve Reduction

E.M.F OF A GALVANIC CELL OR CELL POTENTIAL:

A galvanic cell generally consists of two single electrodes called as half cells. E.M.F is the
driving force responsible for the flow of electricity from cathode to anode.

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 The potential difference which causes the current to flow from the electrode of
higher potential to the electrode of lower potential is known as the cell potential of e.m.f
of the cell.

E.M.F = Ecell = Ecathode - Eanode OR Ecell = Eright - Eleft

OR
Ecell = ER.H.E - EL.H.E OR Ecell = Epositive pole - Enegative pole

CONSTRUCTION AND WORKING OF DANIEL CELL:

CONSTRUCTION:
A zinc rod is dipped in 1M ZnSO4 solution placed in glass vessel which acts as anode and a
copper rod is dipped in 1M CuSO4 solution placed in another glass vessel which acts as the
cathode. The two solutions are connected internally using a salt bridge of saturated KCl
solution and externally using a copper wire.

WORKING:
When the two cells are connected externally the cell functions as follows:
 Zn has the tendency to lose electrons and hence oxidation occurs and acts as anode. The
Zn2+ ions enter the solution and the electrons are left behind on the Zn rod, these electrons
move towards Cu electrode through the external circuit. Thus the Zn rod gets dissolved.

 Cu rod acts as cathode .Cu2+ ions from the CuSO4 solution accepts the electrons donated
from Zn electrode and undergoes reduction. Thus the Cu metal is deposited on the copper
electrode.
 The potential difference causes the electrons to flow from Zn rod to Cu rod through the
external circuit and the electricity flows from Cu rod to Zn rod, because Cu electrode has
higher potential and Zn electrode has lower potential.

DANIEL CELL

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CELL REACTIONS:
2+ -
At anode : Zn(s) Zn (aq) + 2e
2+ -
At cathode : Cu (aq) + 2e Cu (s)
2+ 2+
Over all reaction: Zn (s) + Cu (aq) Zn (aq) + Cu(s)

CELL REPRESENTATION:

2+ 2+
Zn l Zn (1M) ll Cu (1M) l Cu

CALCULATION OF E.M.F OF DANIEL CELL:

E 0Zn 2+ /Zn  0.76V and E 0Cu 2+ /Cu  0.34V

E 0cell  E 0cathode  E 0anode
 E 0Cu 2+ /Cu  E 0Zn 2+ /Zn
 0.34V  (  0.76V)
 1.10V

FUNCTIONING OF DANIEL CELL WHEN EXTERNAL VOLTAGE (EEXT) OPPOSING THE

CELL POTENTIAL IS APPLIED:

 Case-1: If an external opposite potential is applied and increased slowly, we find that the
reaction continues to take place till the opposing voltage reaches the value 1.1 V.

 Case-2: If an external opposite potential is applied equal to 1.1 V the reaction stops
altogether and no current flows through the cell.

 Case-3: If an external opposite potential is applied greater than 1.1 V the reaction again
starts but in the opposite direction and now functions as an electrolytic cell.

Case-1 Case-2 Case-3

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MEASUREMENT OF ELECTRODE POTENTIAL:
The potential of individual half-cell cannot be measured. We can measure only the difference
between the two half-cell potentials that gives the e.m.f of the cell. If we arbitrarily choose the
potential of one electrode (half- cell) then that of the other can be determined with respect to
this.
To measure the electrode potential of an individual half cell a reference
electrode called standard hydrogen electrode is made used, whose electrode potential is
conventionally taken as zero.

STANDARD HYDROGEN ELECTRODE:

It is a primary reference electrode used to measure the electrode potential (SRP/SOP)

of other electrodes.

CONSTRUCTION AND WORKING OF STANDARD HYDROGEN ELECTRODE:

SHE consists of platinum foil freshly coated with platinum black. It is welded to the bottom of
narrow glass tube through a platinum wire. A few drops of mercury are placed in the glass
tube. A copper wire is dipped in mercury to make contact with the external circuit. The narrow
glass tube is surrounded by an outer cylindrical glass jacket having an inlet tube at the top and
holes in the bell shaped bottom.
The platinum foil is kept immersed in exactly 1M hydrochloric acid solution.
The temperature is maintained during the measurement at 298K. Then, pure and dry hydrogen
gas is passed into the jacket under a pressure of one bar. During this, hydrogen gets
adsorbed on the surface of platinum. The excess of hydrogen escapes out. After some time,
equilibrium will be established between the adsorbed hydrogen and H+ ions. This whole
assembly constitutes SHE or NHE (normal hydrogen electrode).

Copper wire
Glass jacket
Pure hydrogen
under 1 bar pressure

Narrow glass tube

Mercury
Platinum foil
1 M HCl acid

STANDARD HYDROGEN ELECTRODE

CELL REACTION:
+ - 1
H (aq) +e / 2H2 (g)

ELECTRODE POTENTIAL = Zero volt (0 V).

DEPARTMENT OF CHEMISTRY 14 SKCH PU COLLEGE

 +
CELL REPRESENTATION:
Pt (S) l H2 (g, 1bar) lH (aq,1M)

LIMITATIONS OF S.H.E:

1. It is difficult to maintain the pressure of H2 gas at 1 bar pressure constantly.

2. It is difficult to maintain the [ H+ ]ions unity (1M) throughout.
3. H2 gas should be pure if not the platinum electrode gets poisoned.
4. Hydrogen is a reducing agent. Hence it cannot be used in presence of an oxidising agent.

DETERMINATION OF SINGLE ELECTRODE POTENTIALS USING THE STANDARD

HYDROGEN ELECTRODE (SHE):

There is no direct method to determine the electrode potentials of single electrodes. However,
single electrode potentials can be determined by an indirect method as follows.

The given electrode whose potential is to be determined is coupled with a reference electrode,
namely, SHE to get a complete cell by using salt bridge. The e.m.f of the cell is determined by
using a potentiometer. Knowing the value of the potential of the reference electrode, that of
the given electrode can be calculated

Example:
1. A pure zinc rod is dipped in 1M zinc sulphate solution. It is a single electrode (a half cell).
It is connected to SHE, a reference electrode by using a salt bridge to get a galvanic cell.
The e.m.f of the cell is determined by using a potentiometer. In this cell the reduction
occurs at SHE and oxidation at zinc electrode. The electrons will flow from zinc electrode
to SHE . The cell is represented in the figure.
Potentiometer

Pure hydrogen
under 1 atm pressure
Salt bridge

Platinum foil
1 M HCl acid

Zinc electrode SHE

Note:
 The direction of flow of conventional current can be determined by connecting a
galvanometer to the circuit.
 The flow of electrons will opposite in direction to the flow of current.
 In place of potentiometer we can also use voltmeter.

DEPARTMENT OF CHEMISTRY 15 SKCH PU COLLEGE

Cell representation: Zn(s) l Zn2+(aq, 1 M) ll Pt(s) l H2 (g, 1 bar) l H+ (aq, 1 M)

Cell reaction: Zn + 2H+ Zn2+ + H2

Emf of the cell:

E 0cell  E 0cathode  E 0anode
0.76V  ESHE
0
 E 0Zn 2+ /Zn
0.76V  0  E 0Zn 2+ /Zn
E 0Zn 2+ /Zn  0.76V

2. A pure copper rod is dipped in 1M copper sulphate solution. It is a single electrode (a half
cell). It is connected to SHE, as said above. In this cell the oxidation occurs at SHE and
reduction at copper electrode. Hence electrons flow from SHE to copper electrode,
therefore, SHE acts as anode and copper electrode as cathode.

Cell representation: Pt(s) l H2 (g, 1 bar) l H+ (aq, 1 M) ll Cu2+ (aq, 1 M) l Cu(s)

Cell reaction: Cu2+ + H2 Cu + 2H+

Emf of the cell:

E 0cell  E 0cathode  E 0anode
0.34V  E 0Cu 2+ /Cu  ESHE
0

0.34V  E 0Cu 2+ /Cu  0

E 0Cu 2+ /Cu  0.34V

IMPORTANCE OF STANDARD ELECTRODE POTENTIAL (E0):

The standard electrode potentials are very important and we can extract a lot of useful information
from them. The values of standard electrode potentials for some selected half-cell reduction
reactions are given in the following table.
1. If the standard electrode potential of an electrode is greater than zero then its reduced form is
more stable compared to hydrogen gas.
2. If the standard electrode potential is negative then hydrogen gas is more stable than the
reduced form of the species.
3. It can be seen that the standard electrode potential for fluorine is the highest in the Table
indicating that fluorine gas (F2) has the maximum tendency to get reduced to fluoride ions
(F–) and therefore fluorine gas is the strongest oxidising agent and fluoride ion is the weakest
reducing agent.
4. Lithium has the lowest electrode potential indicating that lithium ion is the weakest oxidising
agent while lithium metal is the most powerful reducing agent in an aqueous solution.
5. It may be seen that as we go from top to bottom in table the standard electrode potential
decreases and with this, decreases the oxidising power of the species on the left and increases
the reducing power of the species on the right hand side of the reaction.

DEPARTMENT OF CHEMISTRY 16 SKCH PU COLLEGE

STANDARD ELECTRODE POTENTIAL VALUES OF SOME SELECTED HALF-CELL
REDUCTION REACTIONS CALCULATED AT 298 K:

1. A negative E0 means that the redox couple is a stronger reducing agent than the
H+/H2 couple.
2. A positive E0 means that the redox couple is a weaker reducing agent than the
H+/H2 couple.

6. Electrochemical cells are extensively used for determining the pH of solutions, solubility
product, equilibrium constant and other thermodynamic properties and for potentiometric
titrations.

Nernst equation for electrode potential:

Let us consider a cell of the type Mn+ /M which is obtained by dipping the metal ‘M’ in the
solution containing its own ions Mn+
Cell reaction Mn+ + ne- M
The electrode potential for the above cell reaction at any given concentration is given by
Nernst as follows

E (Mn+ /M) = E o (M n+ /M) 

RT
ln
M
nF  M (aq)
n+

 M (s)  = 1
RT 1
E (Mn+ /M) = E o (M n+ /M) - ln
nF  M (aq)
n+

converting ln to log10

DEPARTMENT OF CHEMISTRY 17 SKCH PU COLLEGE

 2.303RT 1
E(Mn+ /M) = Eo(Mn+ /M) - log10
nF  Mn+ 
(aq) 

Where E (M n+ /M) = single electrode potential

E o (M n+ /M) = Standard electro potential

R = Gas constant = 8.314J/k Mole
T = Temperature in Kelvin
n = No. of e- lost/gained /oxidation state of metal
F = Faradays constant = 96500C
[Mn+] = Molar concentration of Mn+

NERNST EQUATION FOR DANIEL CELL

In Daniel cell the electrode potential for Cu2+ and Zn2+ for any given concentration the Nernst
equation can be written as
RT 1
For Cathode: E (Cu 2+ /Cu) = E o (Cu 2+ /Cu)  ln
nF Cu (aq)
2+

RT 1
For Anode: E (Zn 2+ /Zn) = E o (Zn 2+ /Zn)  ln
nF  Zn (aq)
2+

The cell potential,
E (cell) = E (Cu 2+ /Cu)  E Zn 2+ /Zn)

RT 1  RT 1 
E (cell) = E o (Cu 2+ /Cu)  ln   E o
 ln 
nF Cu (aq)   (Zn /Zn) nF  Zn (aq)  
2+
2+ 2+
 
RT  1 1 
E (cell) = E o (Cu 2+ /Cu)  E o (Zn 2+ /Zn)  ln  ln 
nF  Cu (aq)
2+
  Zn (aq)
2+
 
 
RT  Zn (aq) 
2+

E (cell) = E (cell) 
o
ln
nF Cu (aq)
2+


2.303RT  Zn(aq)
2+

E(cell) = E (cell) 
o
log10
nF Cu(aq)
2+


Substituting the values of R, F and T at 298K, we get

o 2.303  8314  298  Zn (aq)

2+

E (cell) = E - log10
2  96500 Cu (aq) 
(cell) 2+

o 0.0591  Zn(aq)
2+

E(cell) = E - log10
Cu(aq) 
(cell) 2+
2

The above equation can be used when temperature in 298K

DEPARTMENT OF CHEMISTRY 18 SKCH PU COLLEGE

CONCLUSION:
1. Ecell depends upon the concentration of both Cu2+ and Zn2+ ions.
2. Ecell increases with increases in conc. of Cu2+ ions or decrease conc. of Zn2+ ions and
vice versa it decreases.
NOTE:
For other electrochemical cells were the oxidation states of the species are different, for them
the no. of electrons (n) used should be same for both the electrodes.
For example: For the following cell
Ni(s) Ni2+(aq)  Ag+(aq) Ag(s)

Cell reaction: Ni + 2Ag+ Ni2+ + 2Ag

2.303RT  Ni(aq)
2+

Nernst equation, E (cell) = E (cell) 
o
log10 2
2F  Ag (aq)
+


For a general reaction, aA + bB cC + dD

2.303RT [C]c [D]d

Nernst equation, E(cell) = Eo (cell)  log10
nF [A]a [B]b
OR
2.303RT [oxidised state]
E (cell) = E o (cell)  log10
nF [reduced state]

EQUILIBRIUM CONSTANT FROM NERNST EQUATION:

If the circuit in Daniel cell is closed the following reaction takes place

2+ 2+
Zn (s) + Cu (aq) Zn (aq) + Cu(s)

As the time passes, the concentration of Zn2+ keeps on increasing while the concentration of
Cu2+ keeps on decreasing. At the same time voltage of the cell as read on the voltmeter keeps
on decreasing. After some time, we shall note that there is no change in the concentration of
Cu2+ and Zn2+ ions and at the same time, voltmeter gives zero reading. This indicates that
equilibrium has been attained. In this situation the Nernst equation is written as:

 2.303RT  Zn 2 
E cell   E 
 cell  log10
nF Cu 2 
 Zn 2 
At equilibrium, E cell   0 and  Constant  K C
Cu 2 
2.303RT
0  Ecell   log10 K C
nF

DEPARTMENT OF CHEMISTRY 19 SKCH PU COLLEGE

 2.303 RT
Ecell   log10 K C
nF
0.0591
at 298K, Ecell   log10 K C
n

Kc for Daniel cell at 298K :

0.0591
Ecell   log K C
n
for Daniel cell, Ecell  1.1V
0.0591
1.1  log K C
2
1.1  2
log K C 
0.0591
K C  antilog 37.288

K C  1.941  1037

Thus, this equation gives a relationship between equilibrium constant of the reaction and
standard potential of the cell in which that reaction takes place. Thus, equilibrium constants of

the reaction which are difficult to measure can be calculated from the corresponding E value
of the cell.
ELECTROCHEMICAL CELL AND GIBBS ENERGY OF THE REACTION:
Electrical work done in one second is equal to electrical potential multiplied by total charge
passed.

Electrical work done, welectrical  Electrical charge  EMF of the cell

welectrical  nF  Ecell
Where,
E(cell) = emf of the cell is
nF = amount of charge passed
If maximum work has to be obtained from a galvanic cell then charge has to be equal to
decrease in its Gibbs energy and therefore

 r G  -nFEcell

Where,  r G = Gibbs energy of the reaction.

DEPARTMENT OF CHEMISTRY 20 SKCH PU COLLEGE

We, know that E(cell) is an intensive property but rG is an extensive property and the value
depends on ‘n’ i.e. number of electrons lost or gained.

Example:
2+ 2+
Zn (s) + Cu (aq) Zn (aq) + Cu(s)

 r G  -2FE cell
But when we write the reaction,
2+ 2+
2 Zn(s) + 2 Cu (aq) 2 Zn (aq) + 2 Cu(s)

 r G  -4FE cell

If the concentration of all the reacting species is unity, then E cell   E cell  and we have

Standard free energy change,  r G 0   nFE cell

0

Thus, from the measurement of Ecell  we can obtain an important thermodynamic quantity,

 r G  , standard Gibbs energy of the reaction.

Note:
 This equation helps us to predict the feasibility/ spontaneity of the cell reaction.
 If  r G   ve , the reaction is spontaneous, the necessary condition is Ecell
0
=   ve
From
 the latter we can calculate equilibrium constant by the equation:

 r G    RT ln K C
OR
 r G    2.303 RT log10 K C

CONDUCTANCE OF ELECTROLYTIC SOLUTIONS:

It is necessary to define a few terms before we consider the subject of conductance of
electricity through electrolytic solutions.
RESISTANCE (R):
It is opposing force offered for the flow of electrons.
The electrical resistance of any object is directly proportional to its length, ‘l’, and inversely
proportional to its area of cross section, ‘a’.

DEPARTMENT OF CHEMISTRY 21 SKCH PU COLLEGE

 1
i.e. R  l and R 
a
l
R 
a
l
R 
a
Where,
ρ (Greek, rho) = Proportionality constant, called as specific resistance or resistivity

 The electrical resistance is represented by the symbol ‘R’

 It is measured in ohm (Ω).
 SI unit = is (kg m2)/(s3 A2).
 It can be measured with the help of a Wheatstone bridge.

SPECIFIC RESISTANCE OR RESISTIVITY (ρ ):

It is the resistance of a material when the length and area of its cross section is unity.
OR
The resistivity for a substance is its resistance when it is one metre long and its area
of cross section is one m2.

 Resistivity is represented by the symbol ‘ρ’ (Greek, rho)

 SI unit = ohm metre (Ω m)
 Other units= quite often its sub multiple, ohm centimetre (Ω cm) is also used.
 IUPAC recommends the use of the term resistivity over specific resistance and hence the
term resistivity is used in further studies.

Conversion:
1 Ω m = 100 Ω cm or 1 Ω cm = 0.01 Ω m

CONDUCTANCE (G):
The inverse of resistance (R) is called as conductance.
1
G 
R
1 a
G  
l 
a
G     where,  specific conductance
l
 Conductance is represented by the ‘G’ or ‘C’.
 SI unit = Siemens (S) or ohm–1 (Ω–1) or mho.

DEPARTMENT OF CHEMISTRY 22 SKCH PU COLLEGE

CONDUCTIVITY /SPECIFIC CONDUCTANCE    :
The inverse of resistivity is called as conductivity or specific conductance.
OR
Conductivity is the conductance of the solution when placed between two electrodes
having an area of cross section of 1 m2 and separated by a distance of 1 m apart.
OR
3
It is the conductance of 1m of the electrolytic solution.
a
we know that, G    
l
l 1
   G  G 
a R
1l l
   R 
Ra a
1 a l
  x x 
 l a
1


 Conductivity is represented by the symbol, κ (Greek, kappa).
 SI unit =S m–1.
 Other units = quite often, conductivity is expressed in S cm–1.
 IUPAC has recommended the use of term conductivity over specific conductance
and hence we shall use the term conductivity in further studies.

THE VALUES OF CONDUCTIVITY OF SOME SELECTED MATERIALS AT 298.15 K:

CONDUCTIVITY CONDUCTIVITY
MATERIAL MATERIAL
(in S m ) –1
(in S m–1)
Conductors Aqueous Solutions
Sodium 2.1×10 3
Pure water 3.5×10–5
Copper 5.9×103 0.1 M HCl 3.91
Silver 6.2×103 0.01M KCl 0.14
3
Gold 4.5×10 0.01M NaCl 0.12
3
Iron 1.0×10 0.1 M 0.1HAc 0.047
Graphite 1.2×10 0.01M HAc 0.016
Insulators Semiconductors
Glass 1.0×10 –16
CuO 1×10–7
Si 1.5×10–2
Teflon 1.0×10–18
Ge 2.0

DEPARTMENT OF CHEMISTRY 23 SKCH PU COLLEGE

It can be seen from the above that the magnitude of conductivity varies a great deal
Factors affecting conductivity;
a. The nature of the material.
b. Temperature and
c. Pressure at which the measurements are made.

CLASSIFICATION OF MATERIALS ON THE BASIS OF MAGNITUDE OF CONDUCTIVITY:

Materials are classified into three types based on the magnitude of their conductivity.
1. Conductors
2. Insulators
3. Semiconductors
 Metals and their alloys have very large conductivity and are known as conductors.
Certain non-metals like carbon-black, graphite and some organic polymers are also
electronically conducting.
 Substances like glass, ceramics, etc., having very low conductivity are known as
insulators.
 Substances like silicon, doped silicon and gallium arsenide having conductivity between
conductors and insulators are called semiconductors and are important electronic
materials.
 Certain materials called superconductors by definition have zero resistivity or infinite
conductivity.
Earlier, only metals and their alloys at very low temperatures (0 to 15 K) were
known to behave as superconductors, but nowadays a number of ceramic materials and
mixed oxides are also known to show superconductivity at temperatures as high as
150K.
Electrical conductance through metals is called metallic or electronic
conductance and is due to the movement of electrons.
The electronic conductance depends on
a) The nature and structure of the metal
b) The number of valence electrons per atom
c) Temperature (it decreases with increase of temperature).

MECHANISM OF ELECTRONIC CONDUCTANCE:

 As the electrons enter at one end and go out through the other end, the composition of
the metallic conductor remains unchanged.
 The mechanism of conductance through semiconductors is more complex (Studied in
solids chapter).

IONIC CONDUCTANCE:
We know that even very pure water has small amounts of hydrogen and
hydroxyl ions (~10–7M) which lend it very low conductivity (3.5 × 10–5 S m–1). When
electrolytes are dissolved in water, they furnish their own ions in the solution hence its
conductivity also increases.

DEPARTMENT OF CHEMISTRY 24 SKCH PU COLLEGE

 The conductance of electricity by ions present in the solutions is called electrolytic
or ionic conductance.
The conductivity of electrolytic (ionic) solutions depends on:
i) The nature of the electrolyte added.
ii) Size of the ions produced and their solvation.
iii) The nature of the solvent and its viscosity.
iv) Concentration of the electrolyte.
v) Temperature (it increases with the increase of temperature).
Passage of direct current through ionic solutions over a prolonged period can
lead to change in its composition due to electrochemical reactions i.e electrolysis takes place.

MEASUREMENT OF CONDUCTIVITY OF ELECTROLYTIC SOLUTIONS:

The Measurement of conductance involves using of Wheatstone bridge method. But
the solution / electrolyte is taken in conductivity cells and then connected to Wheatstone
bridge. However the experimental procedure involves following two steps.
Thus by the determining cell constant and resistance we can evaluate the conductivity.
Accurate measurement of cell resistance can be done using a wheat stone bridge.
However while measuring the resistance of ionic solutions the following two problems are
faced.
1) On passing direct current (DC) the composition of the ionic solution changes.
2) A solution cannot be directly connected to a wheat stone bridge like wire or any
solid substance which is done for electronic conductors.
However the 1st problem is over come by using alternating current (AC) source and the 2nd
problem is over come by using specially designed conductivity cell.

The conductivity cell consists of two platinised platinum electrodes (platinum electrodes
coated with platinum black i.e. finely divided metallic platinum is deposited on the electrodes
electrochemically) separated by distance ‘l’ and has an area of cross section ‘a’. Thus by
knowing the quantity of ‘a’ and ‘l’.The resistance of such a column of solution is then given by
the equation:

DEPARTMENT OF CHEMISTRY 25 SKCH PU COLLEGE

 l 1
R  
a 
l
R
a

Note:
After the construction of the conductivity cell it cannot be directly used for the determination of
resistance of the electrolytic solution, its cell constant is to be determined.

DETERMINATION OF CELL CONSTANT:

CELL CONSTANT:
The ratio of l is called cell constant of the conductivity cell.
a
OR
Cell constant (G*) is defined as the ratio of length between two electrodes (l) and area
of cross section between the electrodes (A).

l
G*  OR G *   R Unit: length-1 S.I Unit: meter-1
a

Note: Measurement of ‘l’ and ‘a’ is not only inconvenient but also unreliable because it cannot
be measured either by using a measuring scale or a measuring tape since the electrode shows
the conductance from all the sides.
Cell constant is usually determined by measuring the resistance of cell whose
conductivity is already known for this purpose KCl solution is used whose conductivity is
accurately known at different temperatures. Once the cell constant is determined, such a cell
can be used for the measurement of resistance or conductivity.

CONDUCTIVITY AND MOLAR CONDUCTIVITY OF KCl SOLUTIONS AT 298.15K:

Molarity Concentration Conductivity Molar Conductivity

mol L–1 mol m–3 S cm–1 S m–1 S cm2mol–1 S m2 mol–1
1.000 1000 0.1113 11.13 111.3 111.3x10-4
0.100 100.0 0.0129 1.29 129.0 129.9x10-4
0.010 10.00 0.00141 0.141 141.0 141.0x10-4

DEPARTMENT OF CHEMISTRY 26 SKCH PU COLLEGE

MEASUREMENT OF RESISTANCE:

R2
Conductivity cell R1

-
-ll
Detector

R3

R4
O
Arrangement for measurement of resistance of an electrolytic solution

The resistance of electrolytic solution can be measured using a wheat stone bridge. It
consists of two resistances R3 and R4, a variable resistance R1 and the conductivity cell of
unknown resistance R2. Wheat stone bridge is provided with an oscillator ‘O’ which is the
source of alternating current (AC) in the audio frequency range of 500-5000 cycles per
second.
A detector ‘P’ is also set in the circuit which is either headphone or any other electronic device.
The bridge gets balanced when no current passes through the detector. Under these
R1 R4
circumstances the unknown resistance will be equal to R2  and thus the conductivity
R3
G*
of solution can be calculated using the formula  
R
The conductivity of solutions of different electrolytes in the same solvent and at a given
temperature differs due to
 Charge and size of the ions in which they dissociate.
 The concentration of ions or ease with which the ions move under a potential gradient.
It, therefore, becomes necessary to define a physically more
meaningful quantity called molar conductivity denoted by the symbol Λm (Greek,
lambda).
..
MOLAR CONDUCTIVITY (Λ m / E m ):
Conductance due to all the ions in a solution containing one mole of the electrolyte is
called molar conductance.
Molar conductivity is related to the conductivity of the solution by the equation:


m 
C
Where,
Λm= molar conductivity,

DEPARTMENT OF CHEMISTRY 27 SKCH PU COLLEGE

 = Conductivity in S m–1
C= concentration in molm-3
Hence, S.I unit= S m2mol-1
Other sub multiple unit = S cm2mol-1

Note:
1 mol m–3 = 1000(L/m3) × molarity (mol/L) and hence,
κ(Scm-1 )
Λ m (Scm 2 mol-1 )=
1000Lm-3×molarity(molL-1 )
If we use S cm–1 as the units for  and mol cm–3, the units of concentration, then the units for
Λm /Ëm are S cm2 mol–1. It can be calculated by using the equation:

κ(Scm-1 ) 1000cm3L-1
Λ m (Scm 2 mol-1 )=
molarity(molL-1 )
Both type of units are used and are related to each other by the equations:
1 S m2mol–1 = 104 S cm2mol–1 OR 1 S cm2mol–1 =10–4 S m2mol–1.


m  if  is expressed in  1m1 and  m in  1m2mol1 or Sm2mol-1
1000 x C
 x 1000
m  if  is expressed in  1cm1 and  m in  1cm2mol1 or Scm2mol-1
C

VARIATION OF CONDUCTIVITY AND MOLAR CONDUCTIVITY WITH CONCENTRATION

(DILUTION):
Both conductivity and molar conductivity changes with change in concentration of the
electrolyte.

VARIATION OF CONDUCTIVITY (  ):
Conductivity decreases on dilution (i.e. with decrease in concentration) for both strong
and weak electrolytes.
Reason: The number of ions per unit volume that carry current in a solution decreases on
dilution.

VARIATION OF MOLAR CONDUCTIVITY (ΛM):

Molar conductivity increases on dilution (i.e. with decrease in concentration) for both
strong and weak electrolytes. (But the increase pattern is different for strong electrolytes
and weak electrolytes)
a
REASON: We know that,  m 
l
On dilution the total volume containing 1 mole of electrolyte increases i.e. ‘a’ increases, since
a =V. But the increase pattern for strong electrolyte and weak electrolyte is different.

DEPARTMENT OF CHEMISTRY 28 SKCH PU COLLEGE

FOR STRONG ELECTROLYTES:
For strong electrolytes molar conductivity increases slowly and steadily with dilution.
REASON:
Strong electrolytes undergo complete dissociation on dissolution, on dilution only
volume factor increases, but the total number of ions remains same.

FOR WEAK ELECTROLYTES:

For weak electrolytes molar conductivity increases steeply with dilution.

REASON:
Weak electrolytes undergo partial dissociation on dissolution, for weak electrolytes on
dilution two factors increases i.e. degree of dissociation of weak electrolytes increases
with dilution hence number of ions increases and volume also increases.
. .o
LIMITING MOLAR CONDUCTIVITY ( E m /  m /  om ):
When concentration approaches zero the molar conductivity is known as limiting molar
conductivity.
OR
Molar conductivity at infinite dilution i.e. at zero concentration is known as limiting
molar conductivity.

RELATIONSHIP BETWEEN MOLAR CONDUCTIVITY (  m ) AND LIMITING MOLAR

CONDUCTIVITY (  m ):
o

FOR STRONG ELECTROLYTES:

It is given by DEBYE-HUCKEL-ONSAGER equation as follows

.. .. o 1 1
E m  E m  AC 2 OR  m   om  AC 2

Where,
A = -slope = constant for a given electrolyte at a given temperature for a given solvent.
If we plot m against C , we obtain a straight line with intercept equal to  m and slope equal
o

to ‘-A’.
The value of the constant ‘A’ for a given solvent and temperature depends on
type of electrolyte i.e. the charges carried by cation and anion produced on dissociation of
electrolyte in the solution. Thus for NaCl, CaCl2, MgSO4…etc. which are known as 1-1, 2-1,
and 2-2 electrolytes respectively. All electrolyte of a particular type have the same values
of ‘A’

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GRAPHICAL INTERPRETATION FOR VARIATION OF MOLAR CONDUCTIVITY WITH
DILUTION:
Variation of molar conductivity with concentration is different for strong and weak electrolytes
as shown in the following plot.

Therefore in such cases  om increases steeply on dilution, especially near lower

concentrations (as shown in the following graph). Therefore,  om cannot be obtained by

extrapolation of  m to zero concentration.

Kohlrausch examined  m values for number of strong electrolytes

o

and observed certain regularities. He noted the difference in  m values of the electrolytes
o

NaX and KX. For any ‘X’ (halogens) difference in the  m values was is nearly a constant.
o

For example at 298K,

. .o . .o . .o . .o . .o . .o
E m( KCl )  E m (NaCl )  E m (KBr )  E m (NaBr )  E m (KI )  E m (NaI )  23.4 S cm 2mol -1

And similarly it was also found that

 om ( NaBr )   om ( NaCl )   om ( KBr )   om ( KCl )  1.8 S cm 2 mol -1
On the basis of above observation he enunciated a law called as KOHLRAUSCH LAW OF
INDEPENDENT MIGRATION OF IONS.
It states that the “limiting molar conductivity of an electrolyte is equal to the sum of the
limiting molar conductivities of individual contribution of the anions and cations of the
electrolyte”.
For example, If  Na
o
 and   are limiting molar conductivity of the sodium and chloride ions
o
Cl

respectively, then the limiting molar conductivity for sodium chloride is given by the equation:
 om ( NaCl )   o ( Na  )   o ( Cl  )

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In general, if an electrolyte on dissociation gives v+ cations and v– anions then its limiting
molar conductivity is given by:

 om    o    o
Here,  and  are the limiting molar conductivities of the cation and anion respectively.
o o

Similarly for CaCl2 it is  om ( CaCl2 )  Ca

o
2  2 
o
Cl

The values of λ0 for some cations and anions in water at 298 K are given in the following
table.
Ion λ o /(S cm 2 mol-1 ) Ion λ o /(S cm 2 mol-1 )
H+ 349.6 OH- 199.1
+ -
Na 50.1 Cl 76.3
+ -
K 73.5 Br 78.1
2+ -
Ca 119.0 CH3COO 40.9
Mg2+ 106.0 SO42- 160.0

FOR WEAK ELECTROLYTES:

Weak electrolytes have lower degree of dissociation at higher concentrations and
hence for such electrolytes, Λm increases with dilution. The increase is due to increase
in the degree of dissociation (α) and consequently the number of ions in total volume
of solution that contains 1 mole of electrolyte increases.
Therefore in such cases  om increases steeply on dilution, especially near lower

concentrations (as shown in the following graph). Therefore,  om cannot be obtained by

extrapolation of  m to zero concentration.

At infinite dilution (i.e., concentration c → zero) electrolyte dissociates completely (α =1), but
at such low concentration the conductivity of the solution is so low that it cannot be measured
accurately. Therefore,  om for weak electrolytes is obtained by using Kohlrausch law of
independent migration of ions.
At any concentration ‘c’, if ‘α’ is the degree of dissociation then it can be
approximated to the ratio of molar conductivity  m at the concentration ‘c’ to limiting molar

conductivity(  om ).

m
 for weak electrolytes
Thus we have,
 om
But we know that, for a weak electrolyte (weak acid) like acetic acid

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  2c
Ka 
1
c 2m
Ka 
2 
 
 om 1  om 
 m 
c 2m
Ka 
 om   om   m 

APPLICATIONS OF KOHLRAUSCH LAW:

1. To calculate  om for any electrolyte from the λo of individual ions.
2. To calculate the dissociation constant value of weak electrolytes (weak acid) like acetic
acid if  om and  m values are know at a given concentration ‘c’.

BATTERIES:
The cell that is used as a source of electrical energy is called as a battery. Basically a
battery is a galvanic cell where the chemical energy of the redox reaction is converted
into electrical energy.
A battery may have one or more than one cell connected in series

GOOD QUALITIES OF A BATTERY:

For a battery to be of practical use
1. It should have reasonably light weight.
2. It should be compact (occupy less space).
3. Its voltage should not vary appreciably during its use.

TYPES OF BATTERIES:
There are mainly two types of batteries.
1. Primary batteries
2. Secondary batteries

PRIMARY BATTERIES:
Batteries in which the reaction occurs only once and after its use over a period of time
the battery becomes dead and cannot be reused again are called as primary Batteries.
Example: Dry cell (also known as Leclanche cell after its discoverer), mercury cell...etc.

DRY CELL / LECLANCHE CELL:

USES: It is commonly used in transistors and clocks.

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STRUCTURE OF THE CELL: It consists of a zinc container that acts as anode and the
cathode is a carbon (graphite) rod surrounded by powdered manganese dioxide (MnO2)
and carbon. The space between the electrodes is filled by a moist paste of ammonium chloride
(NH4Cl) and zinc chloride (ZnCl2).

CELL REACTIONS:
The electrode reactions are complex, but they can be written approximately as follows:
Anode: Zn(s) Zn2+ + 2e–
Cathode: MnO2+ NH4 ++ e– MnO(OH) + NH3

In the reaction at cathode, manganese is reduced from the + 4 oxidation state to the +3 state.
Ammonia produced in the reaction forms a complex with Zn2+ to give [Zn (NH3)4]2+.
Cell potential  1.5 V.

MERCURY CELL:
USES: It is used in low current devices like hearing aids, watches, etc.

STRUCTURE OF THE CELL: It consists of zinc – mercury amalgam as anode and a paste
of HgO and carbon as the cathode. The electrolyte is a paste of KOH and ZnO.
CELL REACTIONS:
Anode: Zn(Hg) + 2OH– ZnO(s) + H2O + 2e–
Cathode: HgO + H2O + 2e– Hg(l) + 2OH–

OVER ALL CELL REACTION:

Zn(Hg) + HgO(s) ZnO(s) + Hg(l )

CELL POTENTIAL  1.35 V

The cell potential remains constant during its life as the overall reaction does not involve any
ion in solution whose concentration can change during its life time.

SECONDARY BATTERIES:
Cells after use can be recharged by passing current through it in the opposite direction
so that it can be used again are called as secondary batteries.

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Example: lead storage battery, nickel-cadmium battery..etc.
Note: A good secondary cell can undergo a large number of discharging and charging cycles.

LEAD STORAGE BATTERY:

Uses: It is commonly used in automobiles and invertors.

STRUCTURE OF THE CELL: It consists of a lead anode and a grid of lead packed with lead
dioxide (PbO2) as cathode. A 38% solution of sulphuric acid is used as an electrolyte.

CELL REACTIONS:
Anode: Pb(s) + SO4 2–(aq) PbSO4(s) + 2e–
Cathode: PbO2(s) + SO4 2–(aq) + 4H+(aq) + 2e– PbSO4 (s) + 2H2O (l)

OVER ALL CELL REACTION:

Pb(s) + PbO2(s) + 2H2SO4 (aq) 2PbSO4(s) + 2H2O(l)
On charging the battery the reaction is reversed and PbSO4(s) on anode and cathode is
converted into Pb and PbO2, respectively

NICKEL-CADMIUM BATTERY:
It has longer life than the lead storage cell but more expensive to manufacture. We shall not
go into details of working of the cell and the electrode reactions during charging and
discharging.

CELL REACTIONS:
The overall reaction during discharge is:
Cd (s) + 2Ni(OH)3 (s) CdO (s) + 2Ni(OH)2 (s) + H2O(l )

Lead storage battery Nickel-cadmium battery

DEPARTMENT OF CHEMISTRY 34 SKCH PU COLLEGE

FUEL CELLS:
INTRODUCTION:
Production of electricity by thermal plants is not a very efficient method and is a major source
of pollution. In such plants, the chemical energy (heat of combustion) of fossil fuels (coal, gas
or oil) is first used for converting water into high pressure steam. This is then used to run a
turbine to produce electricity.
We know that a galvanic cell directly converts chemical energy into electricity
and is highly efficient. It is now possible to make such cells in which reactants are fed
continuously to the electrodes and products are removed continuously from the electrolyte
compartment.
Galvanic cells that convert the energy obtained by combustion of fuels like
hydrogen, methane, methanol, etc. directly into electrical energy are called fuel cells.

One of the most successful fuel cells uses the reaction of hydrogen with oxygen to form water.
This cell was used for providing electrical power in the Apollo space programme. The water
vapours produced during the reaction were condensed and added to the drinking water supply
for the astronauts.
In the cell, hydrogen and oxygen are bubbled through porous carbon electrodes
into concentrated aqueous sodium hydroxide solution. Catalysts like finely divided
platinum or palladium metal are incorporated into the electrodes for increasing the rate of
electrode reactions.

CELL REACTIONS:
Cathode: O2(g) + 2H2O(l ) + 4e– 4OH–(aq)
Anode: 2H2 (g) + 4OH–(aq) 4H2O(l) + 4e–

Overall cell reaction:

2H2(g) + O2(g) 2 H2O(l )

FEATURES:
 The cell runs continuously as long as the reactants are supplied.
 Fuel cells produce electricity with an efficiency of about 70 % compared to thermal plants
whose efficiency is about 40%.
 There has been tremendous progress in the development of new electrode materials,
better catalysts and electrolytes for increasing the efficiency of fuel cells.
 These have been used in automobiles on an experimental basis. Fuel cells are pollution
free and in view of their future importance, a variety of fuel cells have been fabricated and
tried.

DEPARTMENT OF CHEMISTRY 35 SKCH PU COLLEGE

 Fuel cells using H2 and O2 to produce electricity

CORROSION:
Slow coating of surfaces of metallic objects with oxides or other salts of the metal is
called as corrosion.
In corrosion, a metal is oxidised by loss of electrons to oxygen and formation of oxides.
Example: rusting of iron, tarnishing of silver (black coating), development of green coating
on copper and bronze ...etc.

BAD EFFECTS OF CORROSION:

It causes enormous damage to buildings, bridges, ships and to all objects made of metals
especially that of iron. We lose crores of rupees every year on account of corrosion.

CORROSION OF IRON:
Corrosion of iron is commonly known as rusting. It occurs in presence of water and air

CHEMISTRY OF RUSTING OF IRON:

The chemistry of corrosion of iron is quite complex but it may be considered essentially as an
electrochemical phenomenon. At a particular spot of an object made of iron, oxidation takes
place and that spot behaves as anode and we can write the reaction

Anode: 2 Fe (s) 2 Fe2+ + 4 e– E0 (Fe2+/Fe) = – 0.44 V

Electrons released at anodic spot move through the metal and go to another spot on the metal
and reduce oxygen in presence of H+ (which is believed to be available from H2CO3 formed
due to dissolution of carbon dioxide from air into water. Hydrogen ion in water may also be
available due to dissolution of other acidic oxides from the atmosphere). This spot behaves
as cathode with the reaction
Cathode: O2(g) + 4 H+(aq) + 4 e– 2 H2O (l) E0 H+| O 2| H 2O =1.23 V

Overall cell reaction

2Fe(s) + O2(g) + 4H+(aq) 2Fe2 +(aq)+ 2 H2O (l ) E0 (cell) =1.67 V

The ferrous ions are further oxidised by atmospheric oxygen to ferric ions which come out as
rust in the form of hydrated ferric oxide (Fe2O3. x H2O) and with further production of hydrogen
ions.

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PREVENTION OF RUSTING OF IRON:
Prevention of corrosion is of prime importance. It not only saves money but also helps in
preventing accidents such as a bridge collapse or failure of a key component due to corrosion.
One of the simplest methods of preventing corrosion is to prevent the surface of the metallic
object to come in contact with atmosphere. This can be done by
 Covering the surface of the metal with paint, oil, grease or by some chemicals (e.g.
bisphenol).
 Covering the surface of the metal by other metals such as Sn, Zn (galvanisation), etc. that
are inert or react.
 An electrochemical method is to provide a sacrificial electrode (sacrificial protection) of
another metal like Mg, Zn, etc. which corrodes itself but saves the object.

*********

DEPARTMENT OF CHEMISTRY 37 SKCH PU COLLEGE