UNIT 3

ELECTROCHEMISTRY
MARKS = 05

Page 1 of 40

UNIT 3

ELECTROCHEMISTRY
Conductors:
Any substance, which allows the electric current to pass through it, is called an
electrical conductor.
There are two types of conductors.
Types of Conductors
Metallic conductors
Substances, which allow the passage of electricity through them without
undergoing any chemical change.
Example: Cu, Ag, Al etc.
Electrolytic conductors
Substances that allow the passage of electricity through their molten state or
aqueous solutions and undergo chemical decomposition.
Difference between metallic and electrolytic conduction
Metallic Conduction

Electrolytic Conduction

Passage of charge by electrons

Passage of charge by ions in molten

and aqueous state

Passage of charge brings about only

physical changes and does not
involve transfer of matter

Bring about physical and chemical

changes and involves transfer of
matter in the form of ions

Resistance increases with

temperature because of obstacles of
vibrating kernels

Resistance decreases with

temperature because viscosity
decreases

Conducting power is high

Conducting power is low

Page 2 of 40

UNIT 3
Types of Electrolytes
There are three types of electrolytes: Strong, weak and non electrolytes.
Strong electrolytes
A strong electrolyte is one which undergoes complete ionization when
dissolved in water.
The solution contains only the ions and not molecules.
Examples:
HCl, HNO3, H2SO4, NaOH, Ca(OH)2, NaCl, KCl, CH3COONa etc.

Weak electrolytes
A weak electrolyte is one which undergoes partial ionization or dissociation.
Here, in solution the ions and the dissociated molecules will be in equilibrium
with each other. When such a solution is diluted, the degree of ionization
increases. It becomes complete at infinite dilution.
Examples:

HCOOH, CH3COOH, NH4OH, CH3NH2, CH3COONH4, H3PO4 etc.

Non-electrolytes
A substance which doesn't allow the electric current to pass through it is called
a non electrolyte.
These substances have no ions. Therefore they do not ionize in water.
(Covalent compounds).
Examples:

C6H6, toluene, sugar, urea, CH4, C2H6 etc.

Factors Influencing Electrolytic Conduction:

Page 3 of 40

UNIT 3
The inter-ionic attraction
It is the interactions between the ions of the solute at low concentrations. At
low
concentrations the inter-ionic attraction is very less, but at high
concentrations it is appreciable.

The solvation of ions

This interaction is between the ions of the solute and the molecules of the
solvent. Larger the interaction, greater is the solvation, lower will be the
mobility of ions.
Viscosity of the medium
Interaction between the solvent molecules. The solvent-solvent interaction also
lowers the mobility of ions. More the viscosity less is the mobility of ions in the
solution.
Temperature
Ionic mobility increases with increase in temperature, thus conductance
increases.
Increase in temperature also decreases solute-solute, solute-solvent and
solvent-solvent interactions.

Page 4 of 40

UNIT 3

BASIC CONCEPTS
Ohm's law
The potential difference across the conductor is directly proportional to the
current flowing through it.
Solutions obey Ohm's law like metallic conductors.
Resistance (R)
It is the hindrance to the passage of current. It is the ratio of potential
difference (V) across the conductor to the current (I) flowing through it.

It is expressed in ohm.
Conductance (C)
It is the ease provided by a solution to the flow of current.

C is expressed as Ohm-1 or mho or Siemens (S).

Specific resistance
If

R = resistance
l = Length of conductor
a = area of cross section

Then,

= Resistivity or specific resistance.

Page 5 of 40

UNIT 3

Definition of Resistivity or Specific Resistance

It is the resistance offered by 1 cm length of a conductor with area of cross
section of 1 cm2.

Units: ohm.cm

Specific Conductance
It is the reciprocal of specific resistance.

It is the conductance of a solution of 1 cm length having 1 square cm as area

of cross section.

Specific conductance depends upon the concentration of the solution.

Units:

ohm-1 cm-1 or

S/cm-1

l = length of the Conductor

a = Area of cross section of the conductor.

Page 6 of 40

UNIT 3

Equivalent Conductance (^eq.)

It is defined as the conductance of that volume of solution which has one
equivalent dissolved in it.

V = Volume of solution which has one equivalent in it.

N = normality (Number of equivalents per liter or 1000cc)

Molar Conductivity (^m)

It is defined as the conductance of 1 cm3 of volume of electrolyte which has
one mole dissolved in it.
Relation between Equivalent Conductivity and Specific Conductivity
Case I:
In 1 cm3 of the solution containing 1 gm eq. of the electrolyte is taken in the
vessel. The conductance of the solution will be equal to the specific
conductivity and the equivalent conductivity.
Case II:
If 4 cm3 of the solution containing one gram equivalent is taken the equivalent
conductance will still be the conductance of the solution at this dilution. But
now there will be 4 cubes of 1cm 3 each. The specific conductance will be the
conductance of each 1 cm3 of the solution i.e., equivalent conductance will be
four times specific conductance.
Page 7 of 40

UNIT 3

V = Volume of electrolyte which contains one mole in it.

Measurements of Specific Conductivity (k):

Page 8 of 40

UNIT 3

It is not possible to measure l and a accurately.

solution for which specific conductance at 25 oC has been accurately found to

be 0.002765 ohm-1cm-1.
Specific conductance is cell constant multiplied by conductance.

Variation of Molar Conductivity With Concentration:

of electrolytes increases with dilution.
The variation is different for strong and weak electrolytes.
1. Strong Electrolytes:
It is given according to the equation

are the molar conductance at a given concentration and at

infinite dilution (respectively). b is a constant depending on the viscosity of the
solvent. The graph shows that

decreases as the concentration increases.

Page 9 of 40

UNIT 3

This is
at

because
higher

concentration there is greater inter ionic attraction which retards the motion of
the ions as conductance falls
is that conductance at infinite dilution
where the ions are far apart and there is no inter-ionic attraction. This can be
obtained by extrapolation of the graph to zero concentration.
Weak electrolytes:
A weak electrolyte dissociates to a much lesser extent so its conductance is
lower than that of a strong electrolyte at the same concentration.
The very large increase at infinite dilution is because the ionization increases
and so the number of ions in solution increases.
The value of
cannot be obtained by extrapolation as can be seen
on the graph. It is obtained by applying Kohlrausch's law.

Page 10 of 40

UNIT 3

values for strong electrolytes is larger than weak electrolytes for the same
concentration. Increase in
to that for weak electrolyte.

for strong electrolyte is quite small as compared

Kohlrausch's Law:
At infinite dilution when the dissociation of the ions is complete each ion makes
a definite contribution to the total molar conductance irrespective of the nature
of the other ion.
Mathematically,

where
are the molar conductance of A+ and B- at infinite
dilution x and y are the ions provided by one formula unit of the electrolyte.

Applications of Kohlrausch's Law:

1. Calculation of molar conductivity at infinite dilution (o) for weak
electrolytes:
Example: CH3COOH

Page 11 of 40

UNIT 3
The value of
for KCl, CH3COOK and HCl can be obtained by extrapolation
(they are strong electrolytes).

2. Calculation of Degree of Dissociation []

It is defined as the fraction of the total number of molecules undergoing
dissociation at a given concentration.
Example:
If 100 molecules of acetic acid are added to H 2O of which 10 molecules ionise,
then

or
If 0.1M acetic acid has 25% degree of dissociation, what is the concentration of
H2 ion.

For weak electrolytes the increase of molar conductance with dilution is due to
the increase in dissociation.

Page 12 of 40

UNIT 3

3. Calculation Of Dissociation Constant (K):

Degree of dissociation () at a particular concentration C is related to the
dissociation constant (K)

Quantitative Aspect of Electrolysis:

Decomposition of a compound into its constituents by passing electricity is
called electrolysis. It consists of an electrolytic solution in a container. Two
electrodes are dipped in it and they are connected to a battery. When the
electricity is passed, the anion moves to the anode and gets oxidized. This
releases electrons, these electrons pass through the outer circuit, through the
battery and are available at the cathode for reduction of cations.

Faraday's Laws Of Electrolysis:

Page 13 of 40

UNIT 3
Faradays First law of Electrolysis:
The mass of substance deposited is directly proportional to the quantity of
current passed.
If

Wg =
I

=
t =

mass of substance
Current in amperes
time in seconds

electrochemical equivalent.

Z or Electro Chemical Equivalent (ECE) is the mass of substance deposited,

when one Faraday of current is passed for one second.
In other words, when one coulomb of current is passed.
Faradays Second law of Electrolysis:
When the same quantity of electricity is passed through different electrolytes
connected in series the weight of substances deposited at the electrodes is
directly proportional to their equivalent weight.
Example: If CuSO4 and ZnSO4 solutions are connected in series

Alternate statement of the 2nd Law:

To deposit one mole of a substance we must pass an integral number of
Faraday's.
Example:
For one mole of sodium (at. wt 23) = 1F
For one mole of calcium (at. wt 40) = 2F
For one mole of Aluminium (at. wt 23) = 3F
Page 14 of 40

UNIT 3
Galvanic Cells (Voltaic Cell):
It is a device used to convert the chemical energy produced in a redox reaction
into electrical energy.
Example: The redox reaction between Zn and CuSO4 is

If a redox reaction is allowed to take place in such a way that the oxidation half
reaction takes place in one beaker and the reduction half reaction in another
beaker, then electrons will flow from the former to the latter and a current will
flow.

Salt
is

bridge
an

inverted U-tube filled with a strong electrolyte like KCl in Agar-Agar gel.
Anode (Negative terminal) is Zn at which oxidation takes place.

Cathode (positive terminal) is Cu at which reduction takes place.

Page 15 of 40

UNIT 3

Difference between electrochemical cell and electrolytic cell

Electrochemical Cells
It coverts chemical
electrical energy

energy

Electrolytic Cell
into It coverts electrical
chemical energy

energy

into

It is based upon the redox reactions The

reodx
reactions
are
nonwhich are spontaneous
spontaneous and take place only when
energy is supplied
The electrolytes taken in the two Only one electrolyte is taken
beakers are different
Anode is ( ive) at which oxidation Anode is ( + ive) at which oxidation
takes place
takes place
Cathode is ( + ive) at which reduction Cathode is ( ive) at which reduction
takes place
takes place

Construction and Working of an Electrochemical Cell:

A zinc rod is dipped in ZnSO 4 solution and a Cu rod in CuSO 4 solution. The Zn
rod is externally connected to the copper rod through a rheostat, a
galvanometer and a plug key.
Page 16 of 40

UNIT 3

The two aqueous solutions are interlinked through a salt bridge which is an
inverted 'u' tube which is filled with saturated semi solid paste of Agar Agar
saturated in KCl or KNO3 solution.
Note: Agar agar is a carbohydrate which forms a jelly like substance when
dissolved in hot water]
Working:
At the Zn electrode, oxidation takes place:

The 'electrons' (e-) removed or lost by the metal move through the material of
the electrode and reach the Cu electrode at which they are accepted by Cu 2+
ions of the solution to form neutral copper atoms.

In an electrochemical cell, each electrode constitutes one half of the cell and
the reaction taking place at the electrode is called half-cell reaction. The
overall cell reaction is obtained by adding the two half-cell reactions (1) and
(2).

From this it is found that when Zn is added to CuSO 4 solution, Zn displaces Cu

from CuSO4 with the liberation of heat. But in the electrochemical cell there is
no direct contact between Zn and CuSO4. Hence whatever the heat energy that
Page 17 of 40

UNIT 3
would have been liberated appears in the form of electrical energy. Hence the
electrochemical cell acts as a source of current although for a short interval.
The electrode at which oxidation takes place or the metal rod becomes negative
charged is called negative electrode.
The electrode at which reduction takes place or the metal rod becomes positive
charged is called positive electrode.

Accordingly, in the above constructed electrochemical cell, zinc electrode acts

as negative electrode while Cu electrode acts as positive.
The salt bridge:
i.

acts as a link between the two aqueous solution

ii.

overcomes liquid junction potential.

iii.

maintains the electrical neutrality of the aqueous solution of

the electrodes by releasing or sending oppositely charged
ions into the solution.

In general KCl salt bridge is used while KNO 3 salt bridge is used when silver
electrode is involved as one of the electrodes.
Representation of the electrochemical cell:
An electrochemical cell is a device in which oxidation and reduction reactions
take place indirectly and the decrease in the potential energy is converted into
electrical energy.
In representation of an electrochemical cell, the electrode at which reduction
takes place is written on the RHS of the salt bridge and the electrode at which
oxidation takes place is written on the LHS of the salt bridge. The salt bridge
linking the aqueous solutions is represented by two vertical parallel lines
having ions on both sides.
LEFT HAND SIDE

RIGHT HAND SIDE

Anode

Cathode

Oxidation

Reduction

In the above system, Zn electrode is written on the LHS while the Cu electrode
on the RHS of the salt bridge.

Page 18 of 40

UNIT 3

In general, of the two electrodes, the electrode having higher Standard

Reduction Potential (SRP) acts as a positive electrode.
Example:

Zn (s) | Zn2+ (C1)

Metal | Metal ion (Conc.)

|| Cu2+ (C2) | Cu (s)

||

Metal ion (Conc.)

Metal

Where,
C1 and C2 are the concentrations of Zinc (Zn 2+) and Copper (Cu2+) ions
respectively.
Double vertical lines ( || ) represent the salt bridge.

Electrode Potential
Origin of Electrode Potential:
Consider a zinc rod being dipped in ZnSO 4 solution. The zinc atoms on the
surface of the metal with in the solution have tendency to release Zn +2 into
solution retaining the electrons on the surface of the metal. This process is
called dissolution or solution pressure of the metal and it is oxidative in nature.

The zinc ions of the solution have a tendency to accept the electrons on the
surface of zinc rod to form neutral zinc atoms and get deposited on the zinc
rod. This process is called deposition or the osmotic pressure of solution and it
is reductive in nature.
These two processes will be taking place simultaneously at different rates. In
this case, the rate of dissolution is found to be greater than the rate of
deposition. Consequently, by the time equilibrium is reached, more of
dissolution would have occurred and the solution becomes positively charged
whereas rod becomes negatively charged. Due to the attractive electrostatic
forces, the Zn ions accumulate around the Zn rod and an electrical double
layer of opposite charges is formed and between the Zn rod and the solution
the potential developed is called Zinc Electrode Potential

Page 19 of 40

UNIT 3

Consider a copper rod being dipped in CuSO4 solution. Even in this case, both
dissolution and deposition will be taking place simultaneously at different
rates. Here, the rate of deposition is found be greater than the rate of
dissolution. Hence, by the time the equilibrium is reached, the solution
becomes negatively charged while the rod becomes +vely charged. Due to the
attractive electrostatic forces, the negatively ( vely) charged SO 4-2 ions
accumulate around the positively (+vely) charged metal, resulting in the
formation of an electrical double layer. The potential developed at the interface
is called copper electrode potential.
Metal Electrodes:
A metal-ion system in which the metal is in equilibrium with its own ions in
solution is called a metal electrode.
Example:
Zn rod dipped in ZnSO4 solution constitutes a Zn electrode, which is
represented as Zn/Zn+2.
Similarly,
Cu electrode
Iron electrode

Cu/Cu2+
Fe/Fe2+ or

Fe/Fe3+

When equilibrium is established between a gas and its ions in solution a gas
electrode is formed. For this, the gas has to be retained in solution which is
achieved by having a metal like platinum capable of adsorbing the gas and
also should not react with the components of the system. An equilibrium is
established between the gas adsorbed on the metal and the ions of the gas in
solution,.
For example:
Page 20 of 40

UNIT 3
When H2 gas is bubbled through HCl containing a Pt foil, the H 2 gas gets
adsorbed and between the H2 gas on the metal and H+ of the solution, an
equilibrium is established. This constitutes Hydrogen electrode represented as
pt, H2/H+.

(Since the oxide ion in solution forms OH- instead of remaining as O-2).
The Electrical potential difference set up between the metal and its ions in the
solution is called electrode potential.
Or
It may be defined as the tendency of an electrode to lose or gain electrons
when it is in contact with solution of its own ions.
The magnitude of the electrode potential depends on:
1.

Nature of the electrode material.

2.

Concentration of the electrode in the metal ion solution.

3.

Temperature.

Oxidation Potential:
If an electrode undergoes spontaneous oxidation when coupled with a standard
hydrogen electrode (SHE) it is said to have a positive value of oxidation
potential and vice versa.
Reduction Potential:
If an electrode undergoes spontaneous reduction when coupled with a
standard hydrogen electrode (SHE) it is said to have a positive value of
reduction potential and vice versa.
Standard Electrode Potential (Eo)
It is the potential developed when the pure metal is in contact with its ions at
one molar
(1 M) concentration at a temperature of 25oC or 298 K.
Page 21 of 40

UNIT 3
Example:
When a Zn rod of any length is dipped in 1M ZnSO 4 solution, standard
electrode is formed and the potential developed is called standard zinc
electrode potential (EoZn). The standard zinc electrode is represented as
Zn/Zn+2 (1 M).
In case of a gas electrode, the standard electrode potential (E o) is defined as
the potential developed at the interface of the gas and solution containing its
own ions when an equilibrium is established between the gas at a pressure of
760 mm of Hg (1 atm or 1 bar) and the ions in solution of unit concentration (1
M).
When the H2 gas at a pressure of 1 atm is bubbled through HCl of 1 M standard
H2 electrode is formed and the potential developed is called standard hydrogen
electrode potential (E0H2) whose magnitude is considered to be 0.
The standard H2 electrode is represented as
Pt, H2 / H+ (760 mm of Hg)/ (IM)
The magnitude of the standard electrode potential is independent of
temperature since it depends only on the concentration of the ions.
Cell Potential or EMF of a Cell:
The difference between the electrode potentials of two half cells is known as
electromotive force (E.M.F.) or cell potential or cell voltage.
It is represented as Ecell .

Difference between EMF and potential difference

E.M.F.

Potential Difference

E.M.F. is the potential difference when

It is the potential difference under any
no current is flowing through the
condition
circuit
E.M.F.
is
measured
potentiometer

using

a Potential difference can be measured

by a simple voltmeter

Electrochemical Series:
Page 22 of 40

UNIT 3
It is the arrangement of metals in increasing order of standard reduction
potential.
Characteristics of Electrochemical Series:
1.

Reactive metals are placed on top (e.g., Li) and they have a great
tendency to get oxidized. Non-reactive metals like Ag and Au are placed
at the bottom.

2.

Any metal above hydrogen can displace it from dilute acids.

Example:

3.
Any metal which is above another can displace that from its salt
solutions
Example:

4.

If two metals form a cell, the metal that is above undergoes oxidation
and forms the anode while the one below forms the cathode.
Example:
Zn - Anode
(-0.76V)

Cu - Cathode
(+ 0.34V)

Application of Electrochemical Series [ECS]:

1.

Higher the SRP, greater is the tendency to accept e-, higher is the
tendency to get reduced and greater is the oxidizing power. Fluorine
system (F2/F)- has the highest SRP and hence it possesses highest
oxidising power and this increases down the group.

2.

Lower the SRP, lesser is the tendency to accept e-, higher is the tendency
to donate electrons, higher is the tendency to get oxidized and greater is
the reducing power.
Page 23 of 40

UNIT 3
In the ECS, Lithium has the lowest SRP. Hence, it has the highest
reducing power and this goes on decreasing down the series.
3.

Higher the SRP, greater is the tendency to accept e - to form anions,

higher is the electro negative nature. In the ECS, Fluorine system has the
highest SRP and hence it is most electro negative and this goes on
increasing down the series.

4.

Lower the SRP, lesser is the tendency to accept the electrons, greater is
the tendency to donate the e - to form cations and higher is the electro
positive nature. In the ECS, Li system has the lowest SRP and is highly
electro positive which goes on decreasing down the series.

5.

A metal system occurring above H2, displaces H2 from dilute acids, from
water steam depending on its position and gets tarnished.

6.

A metal system occurring below H2 does not displace H2 from dilute

acids, water or steam does not get tarnished.
IN GENERAL:

A metal system with highest SRP

A metal system with lowest SRP

Has highest oxidizing power

Has highest reducing power

More electronegative

More electropositive

Gets displaced by all other systems

above it

Displaces all other systems below it

Always acts as positive electrode

Always acts as negative electrode

Exercise Questions:
Q 1: The electrode potentials A, B, C and D are 2.52 V, 0.16V, + 1.3V and
3.01V
respectively. On the basis of this name the following:
D = 3.01 V
A = 2.52 V
B = 0.16 V
C = + 1.3

V
Page 24 of 40

UNIT 3
(a)
(b)
(c)
(d)
(e)
(f)
(g)
(h)
(i)
(j)
(k)
(l)

Most electropositive
Most electronegative
Highest reducing power
Highest oxidizing power
Lowest oxidizing power
Displaced by all other systems
Does not displace any other system
Displace H2
Always acts as negative electrode
Always acts as positive electrode
System which is not displaced by any other
Which electrode will act as positive and which one as negative in
the following combinations:
i.
ii.
iii.
iv.

A
B
C
D

and
and
and
and

B
C
D
A

A 1:
(a)
Most electropositive
(b)
Most electronegative
:
(c)
Highest reducing power
:
(d)
Highest oxidizing power
:
(e)
Lowest oxidizing power
:
(f)
Displaced by all other systems
(g)
Does not displace any other system:
(h)
Displaces H2
(i)
Always acts as a negative electrode:
(j)
Always acts as positive electrode
(k) System which is not displaced any other
(l)
i.
A is negative and B is positive
ii.
B is negative and C is positive
iii.
D is negative and C is positive
iv.
D is negative and A is positive

:
C
D
C
D
:
C
:
D
:
:

C
D, A and B
C
D

Calculation of Cell Potential:

In an electrochemical cell, electrons flow from negative electrode to the
positive electrode. This shows that there is a potential difference between
the two electrodes.

Page 25 of 40

UNIT 3
The minimum potential which causes the flow of the electrons from the
negative electrode to the positive electrode is called e.m.f.
The emf of a cell is defined as the algebraic difference between the SRP of the
positive electrode and the SRP of the negative electrode even though oxidation
is taking place at the negative electrode.

Standard Reduction Potential of

Cathode

Standard Reduction Potential of

Anode

E0Cathode

E0Anode
OR

ERight or

ER

ELeft or

EL

In general, for a given electrode, the magnitude of oxidation and reduction

potentials remain same but they differ with respect to their signs.
Example:
For a cell made of a zinc electrode in ZnSO4 and copper electrode in CuSO4,

= 0.35 ( 0.76)
= 1.10 V

Nernst Equation:
Effect of temperature and change in electrolytic concentration on electrode
potential is determined by using Nernst equation.
For the reduction reaction,

Page 26 of 40

UNIT 3

Where,
[M]
[M

n+

=
]

Concentration of the metal say M

=

Concentration of oxidized state of the metal.

Electrode potential at concentration Mn+.

E0

Standard electrode potential.

Gas constant

Temperature in K

1 Faraday (96500 coulombs)

Number of electrons involved in the electrode reaction.

For pure solids or liquids or gases at 1 atm. Pressure, the concentration is

taken as unity, i.e., [M] = 1.

R = 8.314 JK-1 mole-1,

F = 96500 coulombs

At T = 298 K,

Example:
Page 27 of 40

UNIT 3
For the Zn - ZnSO4 electrode:

Nernst Equation for EMF of a Cell:

Effect of temperature and concentration on the E.M.F. of a cell
For a general cell reaction:

[Zn] = [Cu] = 1

Equilibrium Constant (Kc) From Nernst Equation:

In the following cell,
Page 28 of 40

UNIT 3
Zn (s) | ZnSO4 (aq) ||

CuSO4 (aq) | Cu(s)

Electrons flow from the Zn to the Cu rod.

1.

Zn from the Zn rod dissolves as Zn2+

2.

Cu2+ from CuSO4 deposits on the Cu plate.

3.

SO42 moves through the salt bridge from CuSO4 to ZnSO4 solution.

The concentration of CuSO4 decreases while that of ZnSO4 increases. As

electrode potential depends upon concentration, a stage comes where both
the electrode potentials are equal. Current stops flowing and the cell is said to
have attained equilibrium.
Example:

The concentration of Cu2+ and Zn2+ at this stage are the equilibrium
concentration.

Significance of Kc
It tells us about the extent to which the reaction has been completed. Kc for
Zn-Cu cell at 298K is 2 x 107 which shows that the reaction has nearly gone to
completion.

Page 29 of 40

UNIT 3
Gibb's Free Energy and Cell Potential (EMF):
When a cell reaction takes place electrical energy is produced which results in
decrease in the free energy of the system.
Electrical work = Decrease in free energy
In an electrochemical cell,
Electric work done =

Quantity of current produced x

E.M.F.

For one mole of electrons quantity of current is 1F (96500 coulomb)

Therefore for n moles it is nF.
Electric work done = n F Ecell

For a standard cell,

For equilibrium,

= RT ln KC

Page 30 of 40

UNIT 3

Predicting Products of Electrolysis from Electrode Potential:

Electrolysis of sodium chloride
1.

Molten sodium chloride:

The only ions present are Na+ and Cl-

2.

Concentrated aqueous sodium chloride:

The products are not the same because water is also involved.

Probable reactions at the cathode

The reduction potential of water is greater so H2 is evolved.

Probable reactions at the anode

The reduction potentials are nearly the same.

Cl2 is preferentially evolved because of
i.
Higher concentration of Cl- ions.
ii.
Over voltage of hydrogen. (Extra voltage required for that reaction
because it
is kinetically slow process)
Actual reactions taking place are:
Page 31 of 40

UNIT 3

3.

Electrolysis of aqueous CuSO4 using platinum electrode:

Comparing the reduction potentials, the actual reactions are

4.

Electrolysis of CuSO4 using copper electrodes:

The actual reactions are:

Note:

If more than one substance is present in an electrolytic cell the substance

liberated at the cathode has highest reduction potential and that at the anode
will have the lowest reduction potential.
Therefore,
i.

Na+, Ca2+ and Al3+ have lower reduction potential than water so H 2 gas is
evolved at the cathode.

ii.

Cu2+, Ag+ have much higher reduction potential than that of water. So
these ions are deposited at the cathode.
Page 32 of 40

UNIT 3

BATTERY
A number of cells connected in series forms a battery.
Primary battery:
In these the redox reactions occur only once and cannot be used again.
Example: dry cells, mercury cells.
Secondary battery:
These can be recharged by passing current and can be used again and again.
Example: Lead storage battery, Ni-Cd storage cell.
Fuel cell:
Energy produced by combustion of fuels like H 2, CO, CH4 can be directly
converted to electric energy.

Primary Cells:
Dry Cells
It is the compact form of the Leclanche cell.
Anode
Cathode

:
:

Cylindrical Zn container.

Central Graphite rod.

The space in between is filled with NH 4Cl and ZnCl2. The graphite rod is
surrounded by MnO2 and carbon.
Reactions:

Voltage: 1.25V to 1.5 V

Page 33 of 40

UNIT 3

It does not have a long life because the acidic NH 4Cl corrodes the Zinc
container.

Mercury

Cell:

Used
in
electric
hearing
watches.

small
devices like
aids
and

Anode
Zinc

:
container

Cathode
Electrolyte :

:
Carbon rod
moist HgO mixed with KOH.

Reactions:

The cell shows a constant potential of 1.35 V throughout as it does not involve
any ion whose concentration changes.

Secondary Cell:
Lead Storage Battery:
Anode

Lead
Page 34 of 40

UNIT 3
Cathode

PbO2

The electrodes are arranged alternately, separated by thin wooden or fibre

glass sheet.
Electrolyte :

dilute H2SO4.

Electrode reaction (during discharging):

Electrode reaction (during charging):

Reverse reactions take place.

Nickel Cadmium storage cell:

Used mainly in calculators.
Anode
Cathode

:
:

Cadmium

NiO2

Reactions:

It can be recharged.

Fuel Cell:
These are devices which convert the energy produced during the combustion
of fuels like H2, CO and CH4 directly into electrical energy. The most successful
Page 35 of 40

UNIT 3
fuel cell is the H2-O2 fuel cell. It was used in the Apollo space programme and
the water produced used as drinking water for the astronauts.
Working:
H2 and O2 are bubbled through a porous carbon rod into concentrated NaOH.
Catalysts are present in the electrodes.

Advantages:
1.

More efficient than conventional cells because the energy of the fuel is
converted directly into electric energy. Efficiency = 60-70%.

2.

They are free from pollution.

CORROSION

Page 36 of 40

UNIT 3
The process of slowly eating away of the metal due to attack of the
atmospheric gases on the surface of metals; forming oxides, carbonates,
sulphides is called corrosion.
For example:

Tarnishing of Ag.
Development of a green coating on Cu and bronze etc.

Corrosion of iron is called rusting

Rust is Fe2O3.xH2O
Rusting is an electrochemical process.
Theory of rusting:
1.

Water on the metal surface dissolves CO2 and O2 from the air.

2.

Fe in contact with dissolved CO2 and O2 undergoes oxidation.

Page 37 of 40

UNIT 3

3.

Electrons lost by Fe are taken by H+

On multiplying the first equation by 4 and adding to the second,

The dissolved O2 can take electrons directly also

4.

Fe2+ reacts with dissolved O2 and water

Rust (Hydrated ferric oxide)

Factors which Promote Corrosion:
1.
2.
3.
4.

Reactivity of metal
Presence of impurities
Presence of air, moisture, gases like SO2 and CO2
Presence of electrolytes

Prevention of Rusting:
1. Barrier protection:
The metal surface is not allowed to come in contact with moisture, O2 and CO2.
i.
ii.
iii.
iv.

Coating the metal surface with paint.

Applying oil or grease.
Electroplating with non-corroding metals like Ni, Cr, Al, Sn, Zn.
Coating with alkaline phosphate (anti rust) solution.
Page 38 of 40

UNIT 3
2. Sacrificial protection:
Covering the surface with a more electro positive metal than Fe. The more
electro positive metal loses electrons and as long as this coating is present Fe
is protected.
Example:
Galvanization

Covering with zinc.

The zinc also forms a protective coating of ZnCO3 . Zn(OH)2.

3. Electrical protection (Cathodic protection):
The iron object is connected to a more active metal either directly or through a
wire. Fe acts as the cathode. The more reactive metal is the anode. It loses
electrons and gradually disappears.
Example: Fe can be connected to Mg, Zn or Al which are called the sacrificial
anodes. Used for protecting under ground pipes from rusting.

(Electrical protection of underground iron pipes)

********************************************************************************
**********************

Important Suggestion:
First of all, prepare Intext &
Exercise Questions as well as Solved Examples from NCERT
Page 39 of 40

UNIT 3
and then only prepare questions from Previous Years
Papers.

Page 40 of 40