A galvanic cell is obtained when two different electrodes are coupled together.

But, all galvanic cells cannot be used as

practical cells or batteries. Generally, the term battery is used for a combination of a few cells of the same type. A practical
battery should have the following characteristics:
1. A practical cell/battery should be light in weight, and compact in size.
2. A practical cell/battery should give a constant voltage. The voltage should not change much during use.
The practical cells/batteries of commercial value are of two types, e.g.,
1. Primary cell/battery [Irreversible]
2. Secondary cell/battery. [Reversible]

Primary Cells
• Primary cells produce electricity by the virtue of chemical reaction. In primary cells,the reaction
occurs only in one direction, and cannot be reversed. As a result these cells become dead over a
period of time.
• Primary cells cannot be recharged/reused.
• Typical primary cells are Daniell cell, Dry cell, and Mercury cell.

Cell Cathode Anode Cell Reaction

Daniell Cell copper vessel zinc rod At anode: Zn(s) →Zn2+(aq) + 2e–
At cathode:Cu2+(aq) + 2e– →Cu(s)
Net cell reaction: Zn(s) + Cu2+(aq) →Cu(s) + Zn2+(aq)
Daniell cell is shown in .The cell may be represented as,
Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)
(anode) (cathode)

Daniell cell gives an emf of 1.1 V.



Salt bridge:

At anode:

At cathode:
 The ammonia molecules formed at the cathode react with Zn2+ ions of ZnCl2 coming from the anode, to form a
complex ion [Zn(NH3)4]2+. If ammonia is not utilized ,the gas get accumulated and disrupts the electric current.

Due to spontaneous chemical reaction.

The ammonia molecules formed at the cathode react with Zn2+ ions of ZnCl2 coming from the anode, to form a
complex ion [Zn(NH3)4]2+. If ammonia is not utilized ,the gas get accumulated and disrupts the electric current.

The chemicals in the dry cells get used over time and the reaction is irreversible.

3. Mercury cells :
 Mercury cells are costlier, and hence used only in sophisticated instruments with low current like camera, hearing
aids, and watches etc.

Cell Cathode Anode Cell Reaction

Mercury cell A paste of Hg, Amalgamated  The electrolyte is a paste of KOH saturated with ZnO
HgO and carbon zinc plate  The reducing agent is zinc and the oxidising agent is mercury
powder acts as anode which is (II) oxide.
the cathode. covered by a  At anode: Zn (Hg) + 2OH– →ZnO + H2O + 2e–
steel top plate.
 At cathode: HgO + H2O + 2e– →Hg + 2OH–

 Overall reaction: Zn (Hg) + HgO(s) →ZnO+ Hg(l)

 As overall reaction does not involve ions, cell potential

remain constant during life time.
 Secondary Cells
 The reaction in a secondary battery occurs many times.
 Once it exhausts it can be recharged and used again.
 They are recharged by passing electric current through it in opposite direction.
 Eg: Lead storage batteries,Ni-Cd cells
Cell Cathode Anode Cell Reaction
1. Lead Storage Battery: Lead PbO2  38% sulphuric acid is used as an electrolyte.

Reactions during discharge:

Anode: Pb(s) + SO42–(aq) --> PbSO4(s) + 2e–
Cathode:
PbO2(s) + SO42–(aq) + 4H+(aq) + 2e– --> PbSO4 (s) + 2H2O (l)
The net cell reaction is:
Pb(s)+PbO2(s)+2H2SO4(aq) --> 2PbSO4(s) + 2H2O(l)

 Since the products are same at cathode and anode

lead storage battery does not require salt bridge.

While charging, the reaction within the battery is reversed

and PbSO4(s) on anode and cathode is converted into Pb
and PbO2, respectively.
[Note: Discharge equation is reversed cathode and anode also
interchanged]
Reactions during charging:
Cathode: PbSO4(s) + 2e– --> Pb(s) + SO42–(aq)
Anode:
PbSO4 (s) + 2H2O (l) --> PbO2(s) + SO42–(aq) + 4H+(aq) + 2e–
The net cell reaction is:
2PbSO4(s) + 2H2O(l)--> Pb(s)+PbO2(s)+2H2SO4(aq)
 Density of electrolyte decreases as water is formed and sulphuric acid is consumed as the product during discharge
of the battery.
2. Nickel-cadmium cell:
 The Nickel-Cadmium battery which is also referred to as the ‘NiCad’ battery.
 It has longer life than lead storage battery.
 It is more expensive.

Cd(s)+ 2Ni(OH)3 (s) ⇔ CdO(s) + 2Ni(OH)2(s) + H2O(l)

 Fuel Cells

Working of Fuel Cell

Advantage:

Suggest two materials other than hydrogen that can be used as fuels in fuel cells.

Methane and methanol can be used as fuels in fuel cells.

Difference Between Rust and Corrosion

Corrosion Rust

Corrosion is the process of deterioration of Rusting is a part of corrosion and is a chemical process which results in the
materials as a result of chemical, electrochemical formation of red or orange coating on the surface of metals.
or other reactions.

Corrosion can occur on different surfaces such as Rusting usually occurs on surfaces of iron , tarnishing of silver, development of
skin, wood, metals, etc. green coating on copper and bronze.

Factors which affect Corrosion

The main factors which affect corrosion are:

(i) Position of metals in e.m.f. series: The reactivity of metal depends upon its position in the electrochemical
series. More the reactivity of metal, the more will be the possibility of the metal getting corroded.

(ii) Presence of impurities in metals: The impurities help in setting up voltaic cells, which increase the speed
of corrosion.

(iii) Presence of electrolytes: Presence of electrolytes in water also increases the rate of corrosion.

(iv) Presence of CO2 in water: Presence of CO2 in natural water increases rusting of iron. Water containing
CO2 acts as an electrolyte and increases the flow of electrons from one place to another.

(v) Presence of protective coatings: When the iron surface is coated with layers of metals more active than
iron, then the rate of corrosion is retarded.

Mechanism of Rusting of Iron

Non-uniform surface of metal or impurities present in iron behave like small electric cells in the presence of water
containing dissolved oxygen or carbon dioxide.

A film of moisture with dissolved CO2, constitutes electrolytic solution covering the metal surface at various places.

In the small electrolytic cells, pure iron acts as anode while cathodes are impure portions.

The overall rusting involves the following steps:

The metal atoms in the lattice pass into the solution as ions, leaving electrons on the metal itself. These electrons
move towards the cathode region through the metal.

At the cathodes of each cell, the electrons are taken up by hydrogen ions (reduction takes place).

The H+ ions are obtained either from water or from acidic substances (e.g CO2) in water:Thus acidic nature
enhances rusting.

Oxidation half reaction

Fe(s) ——-> Fe2+ (aq) + 2e¯] x 2 (EΦ= -0.44 V)

Reduction half reaction

4H+ + O2 +4e¯ ——> 2H2O (EΦ=1.23 V)

Overall cell reaction

2Fe(s) +4H+ +O2 ——–>2Fe2+ (aq) + 2H2O (EΦ =1.67 V)

The ferrous ions are oxidised further by atmospheric oxygen to form rust.

4Fe2+(aq)+O2 (g) + 4H2O ——> 2Fe2O3 + 8H+

Fe2O3 + x H2O ——> Fe2O3·xH2O [Hydrated Iron(III) oxide]

Salt water (sea water) accelerates corrosion. This is mainly due to the fact that salt water increases the electrical
conduction of electrolyte solution formed on the metal surface.

Prevention of Corrosion
This can be prevented or retarded by the methods given below:

1) Barrier protection

The barrier protection can be achieved by any of the following methods :

(i) the surface is coated with paint or some chemicals.

(ii) the surface is protected by applying a thin film of oil or grease.

(iii) the metal is electroplated with metals like tin, nickel, zinc, chromium, aluminium, etc.

Many vehicles such as cycles, motors, cars made from iron sheets are protected from rusting by paints. Many iron
articles are electroplated with coating of other metals.

2) Sacrificial Protection

In this method iron is protected from rusting by covering it with a layer of a metal more active than iron. The
active metal loses electrons in preference to iron and goes into ionic state. This type of process in which rusting of
iron is protected is called sacrificial protection.

Zinc is commonly used for covering iron surfaces. The process of covering iron with zinc is called galvanization.

Zinc undergoes oxidation in preference to iron. Because the reduction potential of zinc is less than the reduction
potential of iron.

Zn2+ (aq) +2e¯ ⇔ Zn(s) EΦ= – 0.76 V

Fe2+ +2e¯ ⇔ Fe(s) EΦ= -0.44 V

In tin plating, i.e., tin coating on iron, the film will be effective as long as it is intact. When scratches occur at the
coating surface both the metals are exposed to oxygen and iron is preferably oxidised and is rusted. This is due to
the fact the reduction potential of tin is more than that of iron.
Sn2+ (aq)+ 2e¯ ⇔ Sn(s) EΦ = -0.4 V

Fe2+ +2e ⇔ Fe(s) EΦ = -0.44 V

3) Electrical protection

This method is used for protecting iron articles which are in contact with water such as underground water pipes.
The article of iron is connected with more active metals like magnesium or zinc. The active metal has lower
reduction potential than iron and will lose electrons in preference to iron.
For example: magnesium has lower reduction potential than iron:
Mg2+ (aq) + 2e¯ ——–> Mg(s) EΦ = -2.37 V

Fe2+ (aq) + 2e¯ ———>Fe(s) EΦ= -0.44 V

Therefore, magnesium will be oxidised in preference to iron and therefore it will protect iron from being rusted.
4) Using anti-rust solutions

Certain antirust solutions which are alkaline in nature are used.

QUESTIONS:
1. How is pH of brine solution affected when it is electrolyzed?
2. Rusting of Fe is quicker in saline water than in ordinary water.Why.
3. What is the role of zinc chloride in a dry cell?
4. Why dry cell becomes dead even if it is not used?
5. Why mercury cell supplies constant cell voltage?
6. How does the density of the electrolyte change when the lead storage battery is discharged?
7. How alkaline medium inhibit the rusting of iron?
8. Why salt bridge is not required for lead storage battery?
9. Account for the following observations:
(a) In a dry cell, the build up of ammonia gas around the carbon cathode should disrupt the
electric current,but in practice this does not happen.
(b) Ordinary dry cells are not rechargeable.