Faraday's Laws of Electrolysis: Q Quantity of Electricity I × T Where I Is The Current T Time

Faraday’s Laws of Electrolysis
From his experiments, Faraday deduced two fundamental laws which govern the
phenomenon of electrolysis. These are :
1.First Law. The mass of ions liberated at an electrode is directly proportional to the
quantity of electricity i.e. charge which passes through the electrolyte.
2.Second Law. The masses of ions of different substances liberated by the same quantity
of electricity are proportional to their chemical equivalent weights.
If m = mass of the ions liberated,

Q = quantity of electricity = I × t where I is the current
t = time,
then according to the first law m α Q or m = Z Q or m = Z It
where Z is a constant and is known as the electrochemical equivalent (E.C.E.) of the
substance. If Q = 1 coulomb i.e. I = 1 ampere and t = 1 second, then m = Z.
Hence, E.C.E. of a substance is equal to the mass of its ions liberated by the passage of
one ampere current for one second through its electrolytic solution or by the passage
of a charge of one coulomb.
The constant Z is composite and it depends on the valency
and atomic weight of the substance concerned.
The opposing e.m.f. which is produced in an electrolyte due to

the absorption of gaseous ions by the electrolyte from the two
electrodes is known as the back e.m.f. of electrolysis or
polarization.
Eq = JHZq or E = JHZ
H kcal be the amount of heat energy absorbed

Electrochemical equivalent of hydrogen is Z kg/coulomb
Primary Cells
• Cells that can not be recharged are called

primary cells.
• They go flat when the cell reaction reaches
equilibrium and you have to buy a
replacement.
• The products slowly migrate away from the
electrodes and are consumed by side
reactions occurring in the cell.
• An electric battery consists of a number of electrochemical cells,
connected either in series or parallel.
• A cell, which is the basic unit of a battery, may be defined as a power
generating device, which is capable of converting stored chemical energy
into electrical energy.
The examples of primary cells are Leclanche cell, zinc-chlorine cell, alkaline-
manganese cell and metal air cells etc.
• If, on the other hand, energy is induced in the chemical substances by

applying an external source, it is called a secondary cell or rechargeable
cell. A battery made out of these cells is called a secondary battery or
storage battery or rechargeable battery.
Examples of secondary cells are lead-acid cell, nickel-cadmium cell, nickel-

iron cell, nickel-zinc cell, nickel-hydrogen cell, silver-zinc cell and high
temperature cells like lithium-chlorine cell, lithium-sulphur cell,
sodium-sulphur cell etc.
The zinc-carbon dry cell
• The first mass-produced and
widely used small-scale
source of electrical energy.
• Has changed very little in the
last 100 years.
• An electrolyte composed of
a moist paste of zinc chloride
and ammonium chloride
plays the same role as the
salt bridge.
• At the anode (-) oxidation of the zinc case
produces electrons:
Zn(s) → Zn2+(aq) + 2e-
• At the cathode (+) Manganese dioxide is
reduced in a complicated reaction that is
thought to be:
2MnO2(s) + 2NH4+(aq) + 2e- → Mn2O3(s) + 2NH3(aq) + H2O(l)
• A new cell produces about 1.5 volts, but this
diminishes significantly during use.
• To maintain a net forward reaction, the soluble
reaction products must migrate away from the
electrodes.
• During use the build up of products around the
electrodes slows and can even stop the forward
reaction.
• This is known as polarisation. If the cell is allowed
to rest, the products migrate away from the
electrodes and the cell can recover.
Alkaline cells
• The alkaline cell is
optimised for
performance and
longevity.
• The alkaline cell is
designed for more
high capacity use
appliances than the
zinc- carbon dry cell.
Alkaline cells
• At the anode Zinc powder around the central
metal rod is oxidised:
Zn(s) → Zn2+(aq) + 2e-
• Once formed, Zn2+ reacts immediately with OH-
ions in the electrolyte to form zinc hydroxide. The
overall reaction at the anode is therefore written
as:
Zn(s) + 2OH-(aq) → Zn(OH)2(s) + 2e-
• At the cathode Manganese dioxide is reduced:
2MnO2(s) + H2O(l) + 2e- → Mn2O3(s) + 2OH-(aq)
Alkaline cells
• They have about 5 times the life of a zinc-
carbon dry cell.
• There is no build up of electrolyte so no ‘rest’
time is needed.
• They are slightly more expensive but offer
better value for money.
Lead-acid Battery
A battery consists of a number of cells and each cell of the battery-consists of (a) positive
and negative plates (b) separators and (c) electrolyte, all contained in one of the many
compartments of the battery container.
•Plates..
•Separators.
•Electrolyte.
•Container.
DISCHARGING
•When the cell is fully charge, its positive plate or anode is
PbO2 and the negative plate or cathode is Pb.
•When the cell discharges i.e. it sends current through the
external load, then H2SO4 is dissociated into positive H2 and
negative SO4 ions.
•As the current within the cell is flowing from cathode to
anode, H2 ions move to anode and SO4 ions move to the
cathode.
•At anode (PbO2), H2 combines with the oxygen of PbO2 and
H2SO4 attacks lead to form PbSO4.
PbO2 + H2 + H2SO4 ⎯→ PbSO4 + 2H2O
At the cathode (Pb), SO4 combines with it to form PbSO4

Pb + SO4 ⎯→ PbSO4
It will be noted that during discharging :
(i) Both anode and cathode become PbSO4
(ii) Due to formation of water, specific gravity of the acid
decreases.
(iii) Voltage of the cell decreases.
(iv) The cell gives out energy.
CHARGING
When the cell is recharged, the H2 ions move to cathode and SO4 ions go to
anode and the following changes take place :
At Cathode PbSO4 + H2 ⎯⎯→ Pb + H2SO4
At Anode PbSO4 + 2H2O ⎯⎯→ PbO2 + 2H2SO4
Hence, the anode and cathode again become PbO2 and Pb respectively.
(i) The anode (PbO2) and cathode (Pb).
(ii) There is arise in voltage.
(iii) Energy is absorbed by the cell.
The charging and discharging of the cell can be represented by a single
reversible equation given below :
For discharge, the equation should be read from left to right and for charge
from right to left.
Nickel-Cadmium Batteries
1. Ni(OH)4 for the positive plate exactly as in the nickel-iron cell.
2. A mixture of cadmium or cadmium oxide and iron mass to
which is added about 3 per cent of solar oil for stabilizing the
electrode capacity. The use of cadmium results in reduced
internal resistance of the cell.
3. the electrolyte is the same as in the nickel-iron cell.
Two Efficiencies of the Cell
The efficiency of a cell can be considered in two ways :
1. The quantity or ampere-hour (Ah) efficiency
2. The energy or watt-hour (Wh) efficiency
Current Capacity, Cell Rating (Self-study)

Charging Systems
(i)The Constant-current System
(ii)The Constant-voltage System.

Maintenance of Lead-acid Cells
The following important points should be kept in mind for keeping
the battery in good condition:
1. Discharging should not be prolonged after the minimum value of
the voltage for the particular rate of discharge is reached.
2. It should not be left in discharged condition for long.
3. The level of the electrolyte should always be 10 to 15 mm above
the top of the plates which must not be left exposed to air.
Evaporation of electrolyte should be made up by adding distilled
water occasionally.
4. Since acid does not vaporize, none should be added.
5. Vent openings in the filling plug should be kept open to prevent
gases formed within from building a high pressure.
6. The acid and corrosion on the battery top should be washed off
with a cloth moistened with baking soda or ammonia and water.
7. The battery terminals and metal supports should be cleaned
down to bare metal and covered with Vaseline or petroleum jelly.

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Faraday’s Laws of Electrolysis

If m = mass of the ions liberated,

The opposing e.m.f. which is produced in an electrolyte due to

H kcal be the amount of heat energy absorbed

• Cells that can not be recharged are called

• If, on the other hand, energy is induced in the chemical substances by

Examples of secondary cells are lead-acid cell, nickel-cadmium cell, nickel-

PbO2 + H2 + H2SO4 ⎯→ PbSO4 + 2H2O

At the cathode (Pb), SO4 combines with it to form PbSO4

Current Capacity, Cell Rating (Self-study)

(ii)The Constant-voltage System.

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