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ELECTRO CHEMISTRY
Electro Chemistry : Electro Chemistry is the study of the processes involved
in the inter conversion of Electrical energy & chemical energy.
Conductor : A substance which allows electric current to pass through it is
called a ‘ Conductor ’.
Eg:- All metals, graphite, fused salts, aqueous solutions of acids, bases & salts.
Conductors are of two types :-
1. Electronic Conductors (or) Metallic Conductors: These are the substances
which conduct electricity, but are not decomposed by it.
Eg: All metals, graphite etc.
2. Electrolytic Conductor (or) Electrolyte: It is a substance which in aqueous
solution or in molten state (or fused state) liberates ions and allow electric
current to pass through, there by resulting in its chemical decomposition.
Eg: Acids, bases, electrovalent salts (NaCl, AgNO 3 ) etc.
Difference between the Electronic conductors & Electrolytic conductors
Electronic conductors Electrolytic conductors
1. The conductance is due to flow of 1. The conductance is due to flow of
electrons. ions.
2. No chemical change takes place. 2. Chemical change takes place.
3. No transfer of matter takes place. 3. Transfer of matter takes place.
4. The conductance decreases with 4. The conductance increases with
increase in temperature increase in temperature

OXIDATION: The process which involves the loss of electrons by a substance

is termed as ‘Oxidation”.
Eg: Zn(s) Zn2+(aq) + 2e-
The addition of oxygen or Removal of H 2 is also termed as “Oxidation”.

REDUCTION: The process which involves the gain of electrons by a substance

is termed as “Reduction”.

Eg: Cu2+ (aq) + 2e- Cu(s)

The addition of H2 or removal of O2 is also termed as “Reduction”. If a

substance loses electrons, some other substance must be involved in the
reaction to accept these electrons, and vice versa. Thus oxidation and
reduction must always go side-by-side. The overall reaction, obtained by
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adding the oxidation & reduction is called as “Redox or oxidation –Reduction

reaction”.

Zn(s)+Cu2+(aq) Zn2+(aq) + Cu(s)

The reaction in which loss of electrons takes place is called as “Oxidation Half
reaction, & the reaction in which gain of electrons takes place is called as
‘Reduction Half reaction’.

ELECTRODE POTENTIAL:

The electrode potential of a Metal is the measure of tendency of a

metallic electrode to lose or gain electrons, when it is in contact with the
solution of its own ions.

REDUCTION POTENTIAL: The tendency of an electrode to gain electrons when

it is in contact with the solution of its own ions.

Mn+ + ne- M [Reduction ------ gain of electrons]

OXIDATION POTENTIAL: The tendency of an electrode to lose electrons when

it is in contact with the solution of its own ions.

M Mn+ + ne- [Oxidation ---loss of Electrons]

The oxidation & reduction potentials of an electrode must have same

magnitude but opposite signs.

STANDARD ELECTRODE POTENTIAL:

The tendency of an electrode to lose or gain electrons when it is in contact

with the solution of its own ions of unit molar concentration (or 1 atm pressure
in case of gas electrode) at 25˚C is called the ‘STANDARD ELECTRODE
POTENTIAL’.

ELECTROCHEMICAL CELLS : An electrochemical cell is a device capable

of either generating electrical energy from chemical reactions and facilitating
chemical reactions through the introduction of electrical energy.

Oxidation-reduction or redox reactions take place in electrochemical

cells. There are two types of electrochemical cells. Spontaneous reactions
occur in galvanic (voltaic) cells; non-spontaneous reactions occur in
electrolytic cells. Both types of cells contain electrodes where the oxidation
and reduction reactions occur. Oxidation occurs at the electrode termed
the anode and reduction occurs at the electrode called the cathode.
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ELECTROLYTIC CELL : An electrolytic cell is an electrochemical cell that

undergoes a redox reaction when electricity is applied. It is most often used
to decompose chemical compounds, in a process called ‘electrolysis’.

Eg: Electrolysis of molten NaCl.

In the electrolysis of molten NaCl, a source of direct current is connected

to a pair of inert electrodes immersed in molten NaCl. As the salt has been
heated until it melts, the Na+ ion flow towards the negative electrode
(Cathode) and the Cl¯ ions flow towards the positive electrode (anode).When
Na+ ions collide with the negative electrode, the battery carries a large enough
potential to force these ions to pick up electrons to form sodium metal. Cl¯
ions that collide with the positive electrode are oxidized to Cl 2 gas, which
bubbles off at this electrode.

{Oxidation} - Anode (+) : 2Cl¯ → Cl2 + 2e¯ (-1.36 V)

{Reduction} - Cathode (-) : 2Na+ + 2e¯ → 2Na (-2.71 V)

Net : 2NaCl(l) → 2Na(s) +Cl2 (g) ( E˚= -4.07 V )

So, the battery used to drive this reaction must therefore have a potential of
at least 4.07 V.

GALVANIC CELL:
A galvanic cell (or a Voltaic cell) is an electrochemical cell that converts the
chemical energy of a spontaneous redox reactions into electrical energy.
A Galvanic cell is made up of two half cells and are corresponding to
oxidation reaction and hence called as ‘Oxidation Half Cell’
Zn → Zn2+ + 2e- (Anode)
and the other corresponding to reduction reaction and hence called as
‘Reduction Half Cell’.
Cu2+ + 2e- → Cu (cathode)
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The two electrodes of half cells are joined by a copper wire through a volt
meter and the electrolytes are joined by salt bridge.
Salt Bridge & its Role:
It is an inverted ‘U’ tube filled with Agar-Agar gel containing a saturated
solution of KCl or KNO3 or NH4NO3 etc.
It does not react with the electrolytes but prevents the accumulation of
charges of the electrodes. It allows the passage of ions from one electrolyte
to the other there by facilitating the continuous production of electricity. It
maintains the electrical neutrality.
In a galvanic cell a spontaneous redox reaction takes place. During the
reactions at anode and cathode, the free energy of the reactants decreases
and appears in the form of electricity.
Construction & working of Galvanic Cell:
It consists of Zn electrode dipped in
ZnSO4 solution which acts as anode
(Oxidation takes place)& Cu electrode
dipped in CuSO4 solution which act as
cathode (Reduction takes place).The
two electrodes joined by a copper wire
through a volt meter and the two
electrolytes are joined by salt bridge
to complete the cell.
The following reactions take place at the electrodes:
At Anode : Zn (s) → Zn2+ (aq) +2e-
At cathode: Cu2+ (aq) + 2e- → Cu (s)
Cell reaction: Zn (s) + Cu2+ (aq) → Zn2+ (aq) + Cu (s)

Representation of a galvanic cell (or) CELL NOTATION:

A Galvanic cell can be represented by the following sign conventions or cell
notation:
1. Anodic half cell should be represented on the left side & the cathodic half
cell should be represented on the right side.
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2. Anodic half cell is represented by writing the symbol of the metal followed
by the symbol of the electrolyte with its concentration in the brackets and the
two are separated by a vertical line or a semicolon.
Zn│Zn2+(C1) or Zn : Zn2+ (C1) or Zn; Zn2+(1M) or Pt , H2 (1atm); H+ (1M)

3. Cathodic half cell is represented by writing the symbol of the electrolyte

with its concentration in the brackets followed by the symbol of the metal
electrode & the two are separated by a vertical line or a semicolon.
Cu2+│Cu or Cu2+ : Cu or Cu2+(1M) ; Cu or CuSO4(1M)│Cu

4. A salt bridge is indicated by two vertical lines, separating two half cells.
Zn/Zn2+ (1M) ║ Cu2+ (1M) / Cu

EMF of an Electro Chemical cell:

The difference between the reduction potentials of the two half cells of a
galvanic cell is known as ‘emf of a cell’. It is also known as cell potential.
Or
The difference of potential, which causes a current to flow from the electrode
of higher potential to one of lower potential, is called as ‘emf of the cell’.
Ecell = Ecathode – E anode {or Ecell = ER – EL} (Bothe are reduction potentials)
The cell reaction is feasible, if Ecell is ‘+ ve’ and it is not feasible, if Ecell is ‘-
ve’ and if it is not feasible, the electrodes will have to be reversed in order to
bring about cell reaction.
Differences between a Galvanic cell and an Electrolytic cell
GALVANIC CELL ELECROLYTIC CELL

1) It is a device to convert 1) It is a device to convert Electrical

Chemical energy into Electrical energy in to Chemical energy
energy.
2) The redox reactions occuring 2) The redox reactions occuring at the
at the electrodes are electrodes are non-Spontaneous & it
Spontaneous. takes place only when electrical energy
is supplied.

3) The electrodes are of 3) The electrodes used may be

dissimilar metals. dissimilar or of the same metal.

4) Each electrode is inserted in 4) Both the electrodes are inserted in

its own ions and both have the same electrolyte solution.
separate compartments.

5) The two electrolyte solutions 5) No salt bridge is needed.

are connected by a salt bridge.
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6) The – ve electrode of the cell 6) The +ve electrode of the cell is an

is an anode. The +ve electrode anode. The - ve electrode of the cell is
of the cell is a cathode. a cathode.

Electrode potentials of metals with respect to SHE (Electrochemical series (or) EMF
series)

Definition: When the various metals are arranged in the order of their increasing values
of standard reduction potential on the hydrogen scale, the arrangement is called the
electrochemical series
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TYPES OF ELECTRODES:
METAL – METAL INSOLUBLE SALT ELECTRODE:
As a standard hydrogen electrode is difficult to prepare and maintain, it is
usually replaced by other reference electrodes, which are known as
‘Secondary reference Electrodes’.
The Metal – insoluble salt electrode consists of a metal (M) in contact with one
of its sparingly soluble salts (MX) and a solution of a soluble salt having a
common anion (X-), with the sparingly soluble salt.
Eg: 1. Calomel Electrode 2. Silver – Silver Chloride Electrode.
1. Calomel Electrode:
It consists of a tube (glass) provided with two narrow side tubes, each on two
sides. At the bottom of the tube, a small amount of Hg liquid of high purity is
placed. It is covered with a paste of Hg + Hg2Cl2 . The remaining portion of
the tube is filled with a solution of KCl (0.1N for deci normal or 1N
for Normal or saturated solution for
saturated calomel electrode SCE).
A platinum wire is sealed in a glass
tube and is dipped in to the liquid
Mercury layer for making electrical
contact with the outer circuit. The
side tube is used for making electrical
contact with the salt bridge.
The electrode is represented as:
Pt, Hg, Hg2Cl2 (s) │KCl (aq)
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The potential of the calomel electrode depends upon the concentration of the
KCl solution.
KCl Concentration 0.1 N 1.0 N Saturated
Electrode potential (V) 0.3335 0.2810 0.2422

Calomel electrode acts as secondary reference electrode.

It acts as either anode or cathode w.r.t the other electrode connected to it.
If the electrode acts as anode, oxidation takes place & the following reactions occur:
2Hg (l) → Hg2 2+ + 2e¯
Hg2 2+ + 2Cl¯ → Hg2Cl2 (s) Oxidation Half reaction, which results
in the decrease of conc. of Cl- ions in
2Hg (l) + 2Cl¯ → Hg2C l2 (s) + 2e¯ the solution

If the electrode acts as cathode, reduction takes place & the following reaction
takes place:
Hg2Cl2 (s) → Hg22+ + 2Cl¯
Hg2 2+ + 2e¯ → 2Hg (s) Reduction Half reaction, which results
in the increase of conc. of Cl- ions in
Hg2C l2 (s) + 2e¯ → 2Hg (s) + 2Cl¯ the solution.

Thus, the Calomel electrode is reversible with respect to Cl - ions.

Measurement of PH using Calomel Electrode:
When connected to SHE, the pH of an unknown solution can be determined
using calomel electrode.
When saturated calomel electrode is connected through the potentiometer to
standard hydrogen electrode dipped in the solution whose p H is to be
determined.
¯
Pt, H2 (1atm)│H+ (unknown) ║ KCl (saturated) │Hg2Cl2 (s)│Hg +
The emf of the cell is
Ecell = Ecathode - Eanode (since EH+/H2 = – 0.0591 pH )
H
Ecell = 0.2422 – (-0.0591 p )
Ecell = 0.2422 + 0.0591 pH
pH = Ecell – 0.2422
0.0591
Advantages:
1. Its construction is very easy.
2. Potential Measurements does not vary with temperature
3. Results of cell potential Measurements are reproducible & stable over a
long period.
Disadvantages:
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1. As Hg2Cl2 degrades at about 50oC, it cannot be used above this

temperature.

3. REDOX ELECTRODES:
A Redox Electrode consists of an inert material like Pt or Au in contact with
the solution of ions of two different oxidation states. The electrode potential
is given by,
E = E˚ + 0.0591 log [aox]
n [ared]
Where aox & ared are activities of the oxidant & reductant.
Eg: 1. ‘Pt’ in contact with Fe+2 & Fe+3 ions of solution.
2. Quinhydrone Electrode

QUINHYDRONE ELECTRODE
The Quinhydrone electrode consists of Pt wire immersed into a solution of
saturated Quinhydrone, which is sparingly soluble in water & is formed by the
combination of equimolar mixture of Quinone (Q) and hydroquinone (QH 2).
It is represented as Pt, Q, QH2; H+(aq) & is reversible with respect to H+
ions

It will either acts as anode or cathode depending on the other electrode

connected to it.
If it acts as cathode, then the electrode reaction is
Q + 2H+ + 2e¯ → QH2
0.0591 [QH2]
EQ = E° Q – log
[Q][H+]2
2
= E° 0.0591 [1] ( since [QH ] = [Q] )
Q – log 2
2 [H+]2
= E°Q + 0.0591 log [H+]
= E°Q − 0.0591 pH
EQ = 0.6994 V – 0.0591 pH ( since E °Q = 0.6994 V )
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Thus, the potential of Quinhydrone Electrode depends upon the P H of the

electrolyte solution with which it is in contact.
Determination of pH using Quinhydrone electrode:
For determining the pH of a solution, the Quinhydrone electrode is connected
to saturated calomel electrode & the emf of the cell produced is determined
potentiometrically. The Quinhydrone electrode acts as cathode (E °=+0.6994
v), While the SCE acts as anode (E° = + 0.2422 v).
Hg (l)│ Hg2Cl2 (s) │ KCl (saturated) ║ H+ (unknown) Q, QH2│Pt
2Hg(l) + 2Cl- (aq) → Hg2 Cl2(S) + 2e- (Oxidation)

Q + 2H+ +2e- → Q H2 (Reduction)

2Hg(l) + Q + 2Cl- (aq) + 2H+ → Hg2Cl 2(S) +QH 2 (cell Reaction)

E cell =E cathode –E anode

= 0.6994 V – 0.0591 pH – 0.2422 V

= 0.4572 V – 0.0591 pH
𝟎.𝟒𝟓𝟕𝟐 𝐕 – 𝐄𝐜𝐞𝐥𝐥
pH =
𝟎.𝟎𝟓𝟗𝟏

Advantages:

1. It is very useful for Acid – Base titrations.

2. Equilibrium is rapidly attained
3. It can be used in presence of ions of Many metals (Zn,Pb,Cu,Sn,Ni etc)
which affect hydrogen electrode
4. It has low internal resistance
5. It is simple & free of errors due to the presence of Non – reducing gases
or salts.
6. Very small quantities of solution are sufficient for the measurement.
Disadvantages:
1. It cannot be used in solutions of pH > 8, since Hydroquinone ionizes as
it is a weak dibasic acid (QH2 → Q-2 + 2H+)
2. It is also oxidized by atmospheric oxygen
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3. It cannot be used in solutions containing Redox systems, which would

react with either Q or QH2.
4. It is not stable for a long time (above 30 o C)
4. ION SELECTIVE ELECTRODES:

The electrodes which have the ability to respond to certain specific ions and
develop a potential with respect to that species only in a mixture are called
‘Ion Selective Electrodes’.
These electrodes use a membrane which is sensitive to particular chemical
species. These are also referred to as ‘membrane electrodes’.
Eg : Glass membrane is H+ ion selective only and does not respond to any
other ion.
GLASS ELECTRODE –It is usually employed for pH measurement.
Construction: It consists of glass bulb made up of special type of glass called
Corning glass (22% Na2O, 6% CaO, and 72% SiO2).It has low melting point
and high electrical conductivity. The glass bulb is filled with 0.1 M HCl solution.
A silver wire coated with AgCl is immersed in it. Ag/AgCl act as internal
reference electrode.
Glass electrode is represented as Ag | AgCl (s) | HCl (0.1M) | glass

Working : when glass electrode is dipped in

the solution whose pH is to be determined
there develops a potential difference between
two surfaces of membrane then the potential
difference developed is proportional to the
difference in pH of the two solutions. Glass
membrane functions as ion exchange resin
and an equilibrium is set up between Na + ions
of glass & H+ ions of solution.

Gl-Na+ + H+ ⇋ Gl-H+ + Na+

The electrode potential of glass electrode can be represented by

EG = 𝑬𝟎𝑮 - 0.0591 pH
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Determination of pH
For the determination of pH of solution, glass electrode is coupled with
saturated calomel electrode and is placed in the solution, whose p H is to be
determined and Ecell is measured. The cell is represented as
Ag|AgCl (s)| HCl (0.1M)| glass |Test solution pH ||KCl (satd.)| Hg2Cl2 | Hg (l)

Ecell =E cathode –E anode or E right –E left

=E ref – EG ( where E ref = Saturated calomel electrode =0.2422 V )

=E ref – ( 𝐸𝐺0 – 0.0591 pH )
=E ref – 𝐸𝐺0 + 0.0591 pH Or pH = Ecell – E ref + 𝑬𝟎𝑮
0.0591
Advantages :
1. Glass electrode is simple & easy to operate,
2. Equilibrium is rapidly attained,
3. The results are accurate and is not easily poisoned,
4. It can be used in coloured, turbid or in colloidal solutions,
5. It can be used both in alkaline and oxidizing solutions.
Limitations :
1. As the resistance of glass electrode is high, potentiometers containing
vacuum tubes are required (Electronic potentiometers).
2. It is used up to a pH range of 0-10. Special glasses can be used to
measure up to 12. If pH >12, glass is attacked by an alkaline solution.
3. It only compares pH values.
NERNST EQUATION :
Nernst derived an expression for the determination of the electrode potential
of any electrode at any concentration is called ‘Nernst Equation’.
From Van’t Hoff reaction isotherm, the free energy change accompanying a
chemical reaction is given by
[Products]
∆ G = ∆ G˚+RT ln - ------------- (1)
[Reactants]
Since ∆ G = -nFE & ∆ G˚ = -nFE˚

[Products]
-nFE = -nFE˚ + RT ln - ------------- (2)
[Reactants]
Dividing Eq (2) by –nF, we get
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RT [Products]
E = E˚ – ln
nF [Reactants]

2.303RT [Products]
= E˚ – log - --------------- (3)
nF [Reactants]

Substituting the values of R = 8.314 JK-1 mol-1 (gas constant)

T = 298 K (Absolute Temperature)
F = 96500 coulombs (Faraday constant)

0.0591 [Products]
E = E˚ – log - ---------------- (4)
n [Reactants]

Where E = Electrode potential,

E˚= Standard Electrode potential
N = no. of Electrons involved in the reaction

For a reaction taking place at the electrode (Reduction)

Mn+ + ne- ⇋ M (or)
Oxidation state + ne- ⇋ Reduced state

˚
0.0591 log [M]
E= E –
n [M𝚗+]
0.0591 log [1]
E= E˚ – (since [M] =1)
n [M𝚗+]
0.0591
E= E˚ + log [Mn+] -------------------------------------- (5)
n
Or At any other temperature ( T ),

𝟐.𝟑𝟎𝟑𝐑𝐓
E = E˚ + log [Mn+]
𝐧𝐅

From this equation,

1) Electrode potential increases as the concentration of the solution [M n+]
increases & vice-versa.
2) Electrode potential increases as the temperature is increased & vice-
versa.
𝟐.𝟑𝟎𝟑𝐑𝐓 [Reduced state]
E = E˚ - log
𝐧𝐅 [Oxidation state]
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For a reaction taking place at the electrode (Oxidation)

M ⇋ Mn+ + ne-
𝚗+
˚
𝟐.𝟑𝟎𝟑𝐑𝐓 log [M ]
E=E –
𝐧𝐅 [M]

𝟐.𝟑𝟎𝟑𝐑𝐓
E = E˚ – log [Mn+] (since [M] =1, for pure solid )
𝐧𝐅

𝟐.𝟑𝟎𝟑𝐑𝐓
E = E˚ – log [Mn+]
𝐧𝐅

Nernst Equation can also be applied to any cell reaction such as

aA + bB ⇋ cC +dD
˚
𝟐.𝟑𝟎𝟑𝐑𝐓 [𝐂]𝐜[𝐃]𝐝
Ecell = E cell – log
𝐧𝐅 [𝐀]𝐚[𝐁]𝐛

Applications of Nernst Equation:

1) Nernst equation is applicable for the study of effect of Electrolyte
concentration on electrode potential
2) It can also be used for the calculation of the potential of a cell under non-
standard conditions
3) The unknown concentration of one of the ionic species in a cell can be
known provided E˚cell and the concentration of other ionic species are known.
4) The PH of a solution can be calculated from emf measurement

Zn
E
Zn
THERMODYNAMICS of EMF of CELL :
In an electrochemical cell, chemical energy is converted into electrical
energy. As, ∆G is the measure of the maximum useful work that can be
obtained from a chemical reaction. Hence
∆G = maximum work
For a cell, whose electrodes differ in potential by ‘E’, the work done when
charge nF is pushed along by the potential of the cell is given by ‘nFE’.
So, maximum work = nFE, where F = Faraday’s constant,
n = no.of electrons transferred
As the electrical energy of a cell is given by the decrease in the free energy (-
∆𝐺), hence
∆G = Wmax = -nFE .................. (1)
From Gibb’s-Helmholtz equation,
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𝛛(∆G)
∆G = ∆H + T [ ]
𝛛T P
Substituting ∆𝐺 in the above equation, we get
𝛛(−nFE) 𝛛𝐸
-nFE = ∆H + T [ ] or -nFE = ∆H - T.nF ( )
𝛛T P 𝛛𝑇 P
𝛛𝐸
or ∆H = -nFE + nFT( )
𝛛𝑇 P
𝛛E
or ∆H = nF [T ( ) − 𝐸]
𝛛T P

comparing the relation with ∆G = ∆H - T∆S or ∆H=∆G + T∆S,

𝛛𝐸 𝛛𝐸
we get , ∆S = nF ( ) ,where ( ) =temperature coefficient of the cell
𝛛𝑇 P 𝛛𝑇 P

BATTERY CHEMISTRY
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Battery: The battery is a device consisting of one or more electrochemical

cells connected with one another in a series that converts stored chemical
energy into electrical energy.
Batteries are broadly divided into 3 types:
(i) Primary Battery (or Primary cell): The battery in which the cell reaction
is not reversible is called ‘ a primary cell’. In primary cell when most of the
reactants have converted to products, the cell no longer produce current and
the cell is said to be ‘dead’.
Eg: Dry Cell (Leclanche cell), Lithium Cell etc.
(ii) Secondary Battery (or Secondary cell): The battery in which the cell
reactions are reversible is called ‘a secondary cell’. These cells can be used
by carrying a large no of cycles of charging & discharging.
Eg: Lead-Acid battery, Lithium ion cell, Ni-Cd battery etc
(iii) Flow Battery ( or Fuel cell ): It is an electro chemical cell that converts
chemical energy into electrical energy, in which materials (reactants,
products, electrolytes) pass through the battery.
Eg: Methanol-Oxygen fuel cell, hydrogen-oxygen fuel cell etc.
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LEAD – ACID BATTERY:

Lead-Acid battery is also called as lead-Acid storage cell and is one that can
operate both as voltaic cell and as an electrical cell.

It consists of spongy lead anode

and lead dioxide cathode . Lead
dioxide is made into paste and
passed into grid, made up of lead.
A no.of lead plates (-ve) are
connected in parallel and a no.of lead
dioxide plates (+ve) are also connected
in parallel. Lead plates fit in between
lead dioxide plates. The plates are
separated by adjacent ones by
insulators like strips of wood, rubber
or glass fibre etc.The entire setup
is immersed in about 20% dil.H2SO4
of density 1.20 to 1.30.
Cell notation : Pb, PbSO4| H2SO4 |PbSO4, PbO2, Pb

Discharging: When cell is operating as voltaic cell then it is said to be

discharging (Supplying of electrical energy)
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Anode: (Oxidation of lead takes place at here) [Lead (-ve)]

Pb → Pb2+ +2e- (Pb2+ combines with SO42- ions of H2SO4 to give PbSO4)
2+ 2-
Pb +SO4 → Pb SO 4 ↓

Pb +SO 42- → Pb SO 4+2e-

Cathode: (PbO2 (+ve)]

PbO2 +4H++2e- → Pb2 + +2H2O The electrons released from the anode
Pb2+ + SO42- → PbSO 4↓ flows to the dioxide electrode. Here Pbo 2
PbO2 +4H +2e + SO42- → PbSO4 2H2O
+ -
gains electrons to form Pb2+. The Pb2+ ions
then combine with SO 42- ions.

So, the net reaction during the discharging is

Pb + PbO2 + 4H+ + 2SO 42- → 2PbSO 4 ↓+ 2H 2O + Energy.

Charging: When both anode and cathode are covered by PbSO 4, the cell
ceases to function as voltaic cell. The cell is then recharged by passing
external emf greater than the cell emf (2volts). Then reverse of the
discharging reactions takes place and anode become cathode and cathode
become anode.

Reaction at Cathode [Pb (-ve) ]: PbSO4 + 2e- → Pb + SO 42-

Reaction at anode [PbO2 (+ve)]: PbSO4 + 2H2O → PbO2 + SO42- + 4H+ + 2e-

Net Reaction during charging is

2 PbSO4 + 2H2O + Energy → Pb + PbO2 + 4H+ + 2SO 42-

During charging the electrodes restore their original conditions and the conc.
of H2SO4 increases, while during discharging the conc. of H 2SO4 decreases.

Generally lead – acid battery is a combination of Six cells in series to form a

battery of 12 volts (2 Volts each)

Uses: To supply current for electrical Vehicles, gas engine ignition, in

telephone exchanges, railway trains, automobiles etc
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Working :Discharging When the lead-acid storage battery operates, the following reaction
occurs.
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Over all reaction:

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3.3 FUEL CELL:

A voltaic cell involves oxidation-reduction reaction. All ordinary combustion reactions are redox
reactions. However, when a fuel is burned, the electron exchange takes place only when the
atoms of the oxidizing agent (oxygen or air) come in direct contact with the atoms of the
substance being oxidized (the fuel). The energy is released principally as heat.
In a fuel cell, electric energy is obtained without combustion from oxygen and a gas that can be
oxidized. Hence, a fuel cell converts the chemical energy of the fuels directly to electricity. The
essential process in a fuel cell is:
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3.6.1 Hydrogen Oxygen fuel cell (or) Alkaline Fuel Cell

Construction  One of the simplest and most successful fuel cell is hydrogen-oxygen fuel cell.

 The alkaline fuel cell or hydrogen-oxygen fuel cell was designed and first demonstrated publicly
by Francis Thomas Bacon in 1939. 
It consists of porous carbon electrodes impregnated with suitable catalyst like finely divided
platinum, or a 73/23 alloy of palladium and silver or nickel.

 Concentrated KOH or NaOH solution is placed between the electrodes to act as electrolyte. For
low-temperature operating fuel battery (-34⁰C to 72⁰C), potassium thiocyanate dissolved in
liquid ammonia is employed.

 The electrodes used here must be: (i) good conductors, (ii) good electron – sources or sinks
and (iii) not be consumed or deteriorated by the electrolyte heat or electrode reactions.

Working 
Hydrogen and oxygen gases are bubbled through the anode and cathode compartment
respectively.

 H2 get oxidized in presence of Pt (electro catalyst) to form H +.

The electrons from anode are absorbed by O2 at cathode which reacts with water from
electrolyte to form OH– ions.
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Disadvantages
1 The corrosiveness of the electrolytes used.
2 It needs to be stored in high tanks.
3: It is difficult to predict the life time of fuel cells accurately.
4: High cost of pure hydrogen and the catalyst needed for the electrode reactions (Ex. Pt, Pd, Ag
etc.,) 
5: Problem of handling gaseous fuels at low temperature or high pressure.
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