Electrolytic production of chlorine and its

uses in water treatment

Chloride is a powerful oxidizing agent with a
standard electrode potential of +1.36V.
Since it has a very high value of standard
electrode potential, very few chemical
oxidizing agents can oxidize chloride ions to
chlorine (Apart from fluorine).
the manufacture of chlorine gas depends on
using electrons themselves.
Chlorine gas is formed during the
electrolysis of molten sodium chloride in
the industrial production of sodium metal.
Chlorine is produced by passing an electric
current through a solution of brine
(common salt dissolved in water). The
chemical term for salt is sodium chloride
(NaCl).
Essential co-products are caustic soda
(sodium hydroxide (NaOH)) and hydrogen
(H
2
). All three are highly reactive, and
technologies have been developed to
separate them and keep them apart
Caustic soda is an alkali and widely-used in
many industries, including the food
industry, textile production, soap and other
cleaning agents, water treatment and
effluent control.
Hydrogen is a combustible gas used in
various processes including the production
of hydrogen peroxide and ammonia as well
as the removal of sulphur fro petroleum
derivatives.
Chlorine has been manufactured industrially
for more than 100 years. During this time,
the industry's firm commitment to the best
safety, health and environmental practices
has ensured continuous improvement.
There are three methods to produce
Chlorine:
The membrane cell process
The diaphragm cell process
The mercury cell process
In the diaphragm cell process
The positive electrode( made of titanium) and negative( made of steel)
electrodes are separated by a permeable diaphragm.
Hydrogen is formed at negative electrode
2H
2
O(l) + 2e
-
H
2
(g) +2OH
-
(ag)
Chlorine is formed at positive electrode
2Cl
-
(ag) Cl
2
(g) +2e
-
The diaphragm is made of asbestos
Sodium chloride solution can flow between the electrodes
Chlorine and hydrogen gas cant flow through( preventing the OH
-
ions
flowing towards the positive electrode)
The Sodium hydroxide solution formed accumulates in the cathode
compartment and is piped off.
The Resulting solution contains about
10% sodium hydroxide
15% unused sodium chloride by mass
The solution is concentrated by evaporation and the sodium chloride
crystallizes out leaving a 50% solution of sodium hydroxide.
Another version of the diaphragm cell is
known as an ions exchange membrane cell.
It uses a partially permeable ion exchange
membrane rather than asbestos. The
membrane is made of a flourinated polymer
and is permeable to positive ions but not
negative ions.
The anode and the cathode are separated by an
ion-exchange membrane. Only sodium ions and a
little water pass through the membrane.
The brine is de-chlorinated and re-circulated. Solid
salt is usually needed to re-saturate the brine.
After purification by precipitation-filtration, the
brine is further purified with an ion exchanger.
The caustic solution(NaOH) leaves the cell with
about 30% concentration and, at a later stage in the
process, is usually concentrated to 50%. The
chlorine gas contains some oxygen and must often
be purified by liquefaction and evaporation.
In the mercury cell process, negative electrode is made of flowing
mercury.
Sodium is above hydrogen in the electrochemical series, sodium is
preferentially discharged as it forms an alloy (known as an amalgam)
with the mercury
Na
+
(ag) + e
-
+Hg(l) Na/Hg(l)
The mercury flows out of the electrolysis cell into a separate
chamber Reacts with water to produce hydrogen and sodium
hydroxide solution
The mercury is recycled back into the electrolytic cell.
Na/Hg(l) +H
2
O(l) Na
+
(ag) + OH
-
(ag) +1/2 H
2
(g) +Hg(l)

The cell is made of PVC-lined steel and the positive electorde where
is chlorine is formed is made of graphite.
2Cl
-
(ag) Cl
2
(g) + 2e
-
As the brine is 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 a
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 impact on the
environment.
In 2007, emissions for all mercury cells across Western
Europe reached an all-time low of 0,97 grammes per tonne of
chlorine capacity.
Forty-two mercury-based chlorine plants remain to be
voluntarily phased out or converted to non-mercury
technology by 2020 at a cost of more than EUR 3,000 million.
These plants account for an ever decreasing part (37.7% in
2007) of European chlorine capacity.

Chlorine's principal applications are in the
production of a wide range of industrial and
consumer products.For example, it is used in
making plastics, solvents for dry cleaning and
metal degreasing, textiles, agrochemicals and
pharmaceuticals, insecticides, dyestuffs, etc.
Chlorine is an important chemical for water
purification (such as water treatment plants), in
disinfectants, and in bleach
Chlorine is usually used (in the form of
hypochlorous acid) to kill bacteria and other
microbes in drinking water supplies and public
swimming pools.
Elemental chlorine is an oxidizer(Chemistry) ,
Weapon (World War I,Irag War),... etc
The mercury cell has been replaced with either diaphragm or
membrane cells in many countries.
The replacement is because of environmental problem since
in practice some of the mercury leaks into the environment
and can build up in the food chain to toxic levels. [ In theory,
all of the mercury is recycled ]
The membrane cell is preferably chosen among three
methods because it is
cheaper to run due to the development of modern polymers.
The consumption of electric energy is the lowest of the three
processes and the amount of steam needed for concentration of
the caustic is relatively small (less than one tonne per tonne of
caustic soda)
Chlorine producers across Europe are progressively moving
towards this method of making their product as the
membrane cell process is the most environmentally sound
way of manufacturing chlorine. In 2007, membrane cell
capacity accounted for 45.6% of total installed chlorine
production capacity in Europe


Besides all of the good uses of Chlorine.
People are also concerned about overusing
of chlorinated organic compounds.
Several of them have been shown to be
carcinogenic(causing cancer)
The C-Cl bond can break homolytically(each atom
getting one of the two electrons) in the presence
of ultraviolet light at higher altitudes to from
chlorine radicals which can contribute to ozone
depletion.
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