The chlor-alkali process is an industrial process for the

electrolysis of sodium chloride solutions. It is the technology used

to produce chlorine and sodium hydroxide (lye/caustic soda),
which are commodity chemicals required by industry.

Usually the process is conducted on a brine (an aqueous solution

of NaCl), in which case NaOH, hydrogen, and chlorine result.
When using calcium chloride or potassium chloride, the products
contain calcium or potassium instead of sodium. Related
processes are known that use molten NaCl to give chlorine and
sodium metal or condensed hydrogen chloride to give hydrogen
and chlorine.
The process has a high energy consumption, for example around
2500 kWh of electricity per tonne of sodium hydroxide produced.
Because the process yields equivalent amounts of chlorine and
sodium hydroxide (two moles of sodium hydroxide per mole of
chlorine), it is necessary to find a use for these products in the
same proportion. For every mole of chlorine produced, one mole
of hydrogen is produced. Much of this hydrogen is used to
produce hydrochloric acid, ammonia, hydrogen peroxide, or is
combusted for power and/or steam production.[
Membrane cell
The most common chloralkali process involves the electrolysis
of aqueous sodium chloride (a brine) in a membrane cell. A
membrane, such as one made from Nafion (Nafion is a brand
name for a sulfonated tetrafluoroethylene based fluoropolymer-
copolymer ), Flemion or Aciplex (Fluorinated Ionomers It was a
perfluorinated ionomer that later became known as Nafion®.
Similar polymers are now being produced by Asahi Glass
(Flemion™) and Asahi Kasei (Aciplex™). These polymers in
membrane form have revolutionized the chlor-alkali industry.), is
used to prevent the reaction between the chlorine and hydroxide
ions.

Basic membrane cell used in the electrolysis of brine. At the

anode (A), chloride (Cl−) is oxidized to chlorine. The ion-selective
membrane (B) allows the counter ion Na+ to freely flow across,
but prevents anions such as hydroxide (OH−) and chloride from
diffusing across. At the cathode (C), water is reduced to hydroxide
and hydrogen gas. The net process is the electrolysis of an
aqueous solution of NaCl into industrially useful products sodium
hydroxide (NaOH) and chlorine gas.
Saturated brine is passed into the first chamber of the cell where
the chloride ions are oxidised at the anode, losing electrons to
become chlorine gas (A in figure):
2Cl− → Cl2 + 2e−
At the cathode, positive hydrogen ions pulled from water
molecules are reduced by the electrons provided by the
electrolytic current, to hydrogen gas, releasing hydroxide ions into
the solution (C in figure):
2H2O + 2e− → H2 + 2OH−
The ion-permeable ion exchange membrane at the center of the
cell allows the sodium ions (Na+) to pass to the second chamber
where they react with the hydroxide ions to produce caustic
soda (NaOH) (B in figure).
The overall reaction for the electrolysis of brine is thus:
2NaCl + 2H2O → Cl2 + H2 + 2NaOH
Diaphragm cell
In the diaphragm cell process, there are two compartments
separated by a permeable diaphragm, often made of asbestos
fibers. Brine is introduced into the anode compartment and flows
into the cathode compartment. Similarly to the Membrane Cell,
chloride ions are oxidized at the anode to produce chlorine, and at
the cathode, water is split into caustic soda and hydrogen. The
diaphragm prevents the reaction of the caustic soda with the
chlorine. A diluted caustic brine leaves the cell. The caustic soda
must usually be concentrated to 50% and the salt removed. This
is done using an evaporative process with about three tonnes of
steam per tonne of caustic soda. The salt separated from the
caustic brine can be used to saturate diluted brine. The chlorine
contains oxygen and must often be purified by liquefaction and
evaporation.
Mercury cell for chloralkali process
In the mercury-cell process, also known as the Castner–Kellner
process, a saturated brine solution floats on top of a thin layer of
mercury. The mercury is the cathode, where sodium is produced
and forms a sodium-mercury amalgam with the mercury. The
amalgam is continuously drawn out of the cell and reacted with
water which decomposes the amalgam into sodium hydroxide,
hydrogen and mercury. The mercury is recycled into the
electrolytic cell. Chlorine is produced at the anode and bubbles
out of the cell. Mercury cells are being phased out due to
concerns about mercury poisoning from mercury cell pollution
(Minamata disease)
Unpartitioned cell
The initial overall reaction produces hydroxide and also hydrogen
and chlorine gases:
2 NaCl + 2 H2O → 2 NaOH + H2 + Cl2
Without a membrane, the OH− ions produced at the cathode are
free to diffuse throughout the electrolyte. As the electrolyte
becomes more basic due to the production of OH−, less
Cl2 emerges from the solution as it begins to disproportionate to
form chloride and hypochlorite ions at the anode:
2 Cl2 + NaOH → NaCl + NaClO + H2O
The more opportunity the Cl2 has to interact with NaOH in the
solution, the less Cl2 emerges at the surface of the solution and
the faster the production of hypochlorite progresses. This
depends on factors such as solution temperature, the amount of
time the Cl2 molecule is in contact with the solution, and
concentration of NaOH.

Likewise, as hypochlorite increases in concentration, chlorates

are produced from them:
3 NaClO → NaClO3 + 2 NaCl
This reaction is accelerated at temperatures above about 60 °C.
Other reactions occur, such as the self-ionization of water and the
decomposition of hypochlorite at the cathode, the rate of the latter
depends on factors such as diffusion and the surface area of the
cathode in contact with the electrolyte.
If current is interrupted while the cathode is submerged, cathodes
that are attacked by hypochlorites, such as those made from
stainless steel, will dissolve in unpartitioned cells.
If producing hydrogen and oxygen gases is not a priority, the
addition of 0.18% sodium or potassium chromate to the
electrolyte will improve the efficiency of producing the other
products.
Electrodes
Due to the corrosive nature of chlorine production, the anode
(where the chlorine is formed) must be non-reactive and has been
made from platinum metal, graphite (called plumbago in
Faraday's time), platinized titanium. A mixed metal oxide clad
titanium anode (also called a dimensionally stable anode) is the
industrial standard today. Historically, platinum, magnetite, lead
dioxide, manganese dioxide, and ferrosilicon (13-15% silicon)
have also been used as anodes. Platinum alloyed with iridium is
more resistant to corrosion from chlorine than pure
platinum. Unclad titanium cannot be used as an anode because
it anodizes, forming a non-conductive oxide and passivates.
Graphite will slowly disintegrate due to internal electrolytic gas
production from the porous nature of the material and carbon
dioxide forming due to carbon oxidation, causing fine particles of
graphite to be suspended in the electrolyte that can be removed
by filtration. The cathode (where hydroxide forms) can be made
from unalloyed titanium, graphite, or a more easily oxidized metal
such as stainless steel or nickel.