ELECTROCHEMISTRY

Commercial Cells
▪ Commercial cells are electrochemical cells which can be used to produce electric
current for practical use.
▪ If a number of cells are connected in series, then it is called a battery.
▪ They are of mainly three types:
1. Primary cells 2. Secondary cells 3. Fuel cells
(1) Primary Cells
▪ They cannot be recharged again.
▪ In primary cells, reaction occurs only once.
▪ After use over a period of time, these become dead and cannot be reused.
▪ Examples: Dry cell (Leclanche cell), Mercury cell

(2) Secondary Cells

▪ Secondary cells can be recharged again.
▪ Here reaction occurs in many times.
▪ A good secondary cell can undergo a large number of charging cycles.
▪ Examples: Lead storage battery, Nickel-cadmium cell

(3) Fuel Cells

▪ Fuel cells are galvanic cells in which the energy of combustion of fuels is directly
converted into electrical energy. Eg: H2-O2 fuel cell
Advantages of fuel cell.
(i) It does not cause any pollution
(ii) It has high efficiency (70%)
The cell reactions taking place in the H2-O2 fuel cell is
▪ At anode: 2H2(g) + 4OH−(aq) → 4H2O(l) + 4e−
▪ At cathode: O2(g) + 2H2O(l) + 4e− → 4OH−(aq)
▪ The overall cell reaction: 2H2(g) + O2(g) → 2H2O(l)
▪ H2-O2 fuel cell was used for providing electricity to the Apollo space programme
 Name of the Anode Cathode Electrolyte Cell
cell voltage
MnO2 + C (touching to cathode)
Dry cell Zn Graphite 1.5 V
NH4Cl + ZnCl2 (touching to anode)

Mercury cell Zn amalgam HgO + C KOH+ZnO 1.35 V

Lead storage
Spongy Pb PbO2 H2SO4 (38%) 2.05 V
battery

Ni-Cd cell Cd NiO2 KOH 1.34 V

Porous carbon
Porous carbon rod
rod through
Fuel cell through which H2 KOH 0.9 V
which O2
passed
passed

Corrosion
It is the process of slow conversion of metals in to their undesirable compounds usually
oxides by reaction with moisture and other gases present in the atmosphere. Examples are
given below.
1. Rusting of iron
2. Tarnishing of silver
3. Green coating on the surface of copper

Rusting of iron
▪ Chemically rust is Hydrated ferric oxide; Fe2O3.xH2O.
▪ Rusting is an electrochemical phenomenon. During rusting, the Fe surface behaves as
an electrochemical cell called corrosion cell or Corrosion couple.
▪ In this corrosion cell, pure Fe act as anode and impure Fe surface act as the cathode.
▪ Moisture having dissolved O2 or CO2 acts as electrolyte.
▪ The following reactions are taking place during rusting
▪ H2O + CO2 → H2CO3;
▪ H2CO3 → 2H+ + CO32
▪ At anode : Fe → Fe2+ + 2e–
▪ At cathode 2H+ + ½ O2 +2 e- → H2O.
▪ Net reaction: Fe + 2H+ + ½ O2 → Fe2+ + H2O
▪ The Fe2+ ion moves through water and comes to the surface of the iron object
where they oxidized to Fe3+ by atmospheric O2 and finally it comes out as rust.
▪ 2Fe2+ + ½ O2 + 2H2O → Fe2O3 + 4H+
▪ Fe2O3 + XH2O →Fe2O3 .XH2O

Prevention from corrosion

1. Barrier protection
Greases, oil paint or any other corrosion resistance are coated on the
surface of the metal so that the metal cannot have direct contact with the air.
2. Sacrificial protection
In this process more reactive metals like Zn is covered on the surface of Fe.
This process of covering Fe with Zn is called galvanization. Since Zn is more
electropositive then Fe is loses e- preferentially and goes into the solution as
Zn2+ ions. So, Fe is not affected as long as Zn is available.
3. Electrical protection/Cathodic protection
Here pieces of Mg, Zn or Al are buried along with underground Fe pipes are
connected to it by insulated wires. Mg, Zn or Al act as anode by losing e-s.
Then Fe become cathode and thus prevents its tendency to corrode by losing e-
4. Anti-rust solution
Alkaline phosphate and alkaline chromate solutions are used for this purpose.
Bisphenol is also used as an anti-rust solution.