CONTENTS

• Acknowledgement
• Working of mercury cell
• Diagram of mercury cell
• Construction of mercuric oxide battery
• Advantages and Disadvantages
• Bibliography
WORKING OF MERCURY CELL

In the mercury cell process, sodium forms an amalgam (a ‘mixture’ of two metals) with the mercury
at the cathode. The amalgam reacts with the water in a separate reactor called a decomposer where
hydrogen gas and caustic soda solution at 50% are produced.

As the brine usually re-circulated, solid salt is required to maintain the saturation of the salt water.
The brine is first de-chlorinated and then purified by a precipitation-filtration process. The products
are extremely pure. The chlorine, along with little oxygen, generally can be used without further
purification.

Of the three processes, the mercury process uses the most electricity, but no steam is required to
concentrate the caustic solution. The use of mercury demands measures to prevent environmental
contamination. Also, mercury must be removed from the hydrogen gas and caustic soda solution.

Mercury losses have been considerably reduced over the years. Increasingly, chlorine producers are
moving towards membrane technology, which has much less effect on the environment.

In 2015, emissions for all mercury cells across Western Europe reached 0.68 grams per tonne of
chlorine capacity, slightly higher than the all-time low of 0.74 grammes per tonne of chlorine capacity
in 2014. After that the mercury process in Western Europe was phased out in 2017.
Construction of Mercuric Oxide Battery

This battery was mainly manufactured in bottom, flat and cylindrical

shape. In the bottom configuration, the top cover of the battery is made of
copper alloy on the inner face and nickel or stainless steel on the outer face.
The top cover is insulated from the bottom container by a nylon grommet.
Amalgamated zinc powder is dispersed inside the top cover. The lower
portion of the container is filled with a mixture of mercuric oxide and
graphite. Graphite helps here to increase the conductivity of mercuric
oxide. The mercuric oxide is the main cathode material of the battery. The
top of the cathode mixture is covered with potassium hydroxide, or
sodium hydroxide electrolyte-soaked porous barrier. Now the whole top
cover along with grommet and anode material is pressed down into the
bottom container. Now the upper portion of the battery is the anode, and
the lower portion is the cathode, and the porous separator contains the
electrolyte in between them. The whole assembly is tightly held together by
crimping the top edge of the bottom can or container. In flat configuration,
zinc powder is amalgamated and pressed into a pellet. The top cover of the
battery is double plated with integrally moulded polymer grommet. The
outer and inner top plates are made of nickel-plated steel, but the inner
plate is tin plated on the inner surface. The main container of the cell is also
made of two nickel plated steel made cans. And the adapter tube is placed
in the space in between the inner and outer can. The lower portion of the
container is filled with cathode mixture, and on the top of the cathode
mixture electrolyte, absorbents are placed. The top grommet assembly
along with anode pallet is pressed into the inner can and seal being done
by crimping over the outer can. A vent hole is provided in the outer can so
that the gas which might be generated during discharge can easily be
escaped between inner and outer cans, any entrained electrolyte being
absorbed by the paper adaptor tube.
Chemistry of Mercuric Oxide Battery
Two types of alkaline electrolyte are used in the zinc / mercuric cell, one
based potassium hydroxide and other is sodium hydroxide. The sodium
hydroxide electrolyte is generally used where low

temperature operation and high current drain are not essential. This
electrolyte is generally used in zinc mercuric oxide cell, whereas potassium
hydroxide-based electrolyte is only used in cadmium mercuric oxide cell.
Cadmium is insoluble in potassium hydroxide solution and that is why the
cadmium mercuric oxide cell is quite suitable for low temperature
operation.

Anode Reaction in Zinc Mercuric Oxide Battery

The anode reaction can be written as,

This reaction can be simplified as,

Anode Reaction in Cadmium Mercuric Oxide Battery

The anode reaction can be written as,

This reaction does not produce any water hence; the electrolyte used in this
cell should have desired high percentage of water.

Cathode Reaction in Mercuric Oxide Battery

The cathode reaction of the battery can be written as,
Rated Voltage of Mercuric Oxide Battery
Open circuit or no-load voltage of zinc mercuric oxide battery is 1.35 V.
This voltage is quite stable under different temperature over a long period
of time. No load voltage of zinc mercuric battery remains within 1% for
several years. This no-load voltage may only vary in the order of 2.5 mV if
the operating temperature of the battery varies from – 20oC to + 50oC. This
battery has flat discharge characteristic, means the battery voltage remains
almost same for prolong discharge period with different currents.

Open circuit voltage of cadmium mercuric oxide battery is 0.9 volt, and it is
quite stable under all operating conditions within a temperature range
from – 55oC to + 80oC. Although operating temperature as high as + 180oC
has been achieved by special deign of the battery.

Storage of Mercuric Oxide Battery

The storage characteristic of this Battery is quite good, and store life is
given in below table,

Period of Temperature of
Capacity loss
Storing Storing

Zinc Mercuric 2 years 20oC 10 to 20%

Oxide Battery 1 years 45oC 20%

Cadmium 10 years 20oC 20%

Mercuric Oxide
Battery 1 years 80oC 15%
Advantages of Zinc Mercuric Oxide Battery
1. It has very high energy density. It is about 450 Wh/L
2. It has a very long storage life.
3. Remains stable under wide range of current density.
4. It is highly electrochemically efficient.
5. It is very robust and generally non sensitive to mechanical impact
and vibration.
6. It gives stable 1.35 V of open-circuit voltage which is an important
advantage of zinc mercuric battery.
7. It gives stable voltage throughout long range of current drain
operating period.

Disadvantages of Zinc Mercuric Oxide Battery

1. These batteries are highly expensive. That is why they have limited
usage.
2. Although the energy to volume ratio of the battery is high but energy
to weight ratio is moderate.
3. Performance of this battery is not very good at low temperature.
4. Due to presence of mercury, disposal of used zinc mercuric oxide
battery creates a problem.
 Bibliography
• NCERT Textbook
• Google
• Dinesh refresher