The chloralkali process (also chlor-alkali and chlor alkali) is an industrial process for the electrolysis of NaCl.

The term
chlor-alkali refers to the two chemicals (chlorine and an alkali) which are simultaneously produced as a result of the
electrolysis of a saltwater. The most common chlor-alkali chemicals are chlorine and sodium hydroxide.

Sodium chloride solution is the salt solution in aqueous form and is also called brine solution.
This means the solution now contains 4 ions, sodium ions, hydrogen ions, chloride and hydroxide ions.
To extract sodium hydroxide, chlorine gas, and hydrogen gas, a current is run through a brine solution in an electrolysis
process. There are three major types of cells used in the electrolysis of brine: the mercury cell, the diaphragm cell, and the
membrane cell.

Diaphragm Cell Electrolysis

A SIMPLIFIED DIAPHRAGM CELL

Obtained from: http://www.chemguide.co.uk/inorganic/group7/diaphragmcell.html
The diaphragm cell is relatively cheap to produce. It is designed to keep the chlorine gas and sodium hydroxide products
separated at the end of the electrolysis process, in order to prevent them from reacting together. If chlorine gas reacts with
hydrogen gas, it produces hydrogen chloride (HCl(g)), which explodes under pressure or exposure to heat. If chlorine gas
reacts with sodium hydroxide, a mixture of sodium chloride (NaCl) and sodium hypochlorite (NaClO), commonly known as
bleach, is produced.
The purpose of chlor-alkali electrolysis is to keep the sodium hydroxide and chlorine gas separate from one another, which
is possible with the diaphragm cell.
The diaphragm cell has two separate sections – one with a titanium anode, and one with a steel cathode. The diaphragm
between the sections is composed of a porous mixture of asbestos and polymers. The solution from the anode
compartment can seep through it into the cathode section. To ensure that liquid flow is always from anode to cathode, there
is a greater volume of solution on the anode side. This prevents any sodium hydroxide solution from returning to where
chlorine gas is being formed.
Chlorine anions are oxidized at the titanium anode to produce chlorine gas:
2Cl–(aq) → Cl2(g) + 2e–
Some of the chlorine is contaminated with oxygen that is formed from the oxidation of hydroxide ions, but it is purified by
liquefying it under high pressure. At high enough pressure conditions, chlorine gas liquefies, while oxygen gas does not
undergo any phase change.
At the steel cathode, hydrogen ions are reduced to form hydrogen gas:
2H+(aq) + 2e– → H2(g)
At the same time, a dilute sodium hydroxide solution is produced at the cathode:
Na+(aq) + e– → Na(l)
Na(l) + H2O(l) → NaOH(aq)
As this solution leaves the cell, it is concentrated through evaporation, in which most sodium chloride crystallizes as solid
salt. This solid salt can be separated, dissolved in water, and once again passed through the cell.
The diaphragm cell does not produce a perfect sodium hydroxide solution, as even after concentration, it will still be slightly
tainted with a small percentage of sodium chloride.

Brine is concentrated sodium chloride solution. If an electric current is passed through it, hydrogen gas forms at the
negative electrode and chlorine gas forms at the positive electrode. A solution of sodium hydroxide forms.
You might have expected sodium metal to be deposited at the negative electrode. But sodium is too reactive for this to
happen, so hydrogen is given off instead.

Electrolysis

Electrolysis of sodium chloride solution

These three products - hydrogen, chlorine and sodium hydroxide - have important uses in the chemical industry:
Hydrogen
 making ammonia
 making margarine
Chlorine
 killing bacteria in drinking water
 killing bacteria in swimming pools
 making bleach
 making disinfectants
 making hydrochloric acid
 making PVC
 making CFC's - limited production
Sodium hydroxide
 making soap
 making paper
 making ceramics

The position of the ion in the electrochemical series

• For eg, in a competition between the two ions the copper ions, if it is present will preferentially pick up the electrons.
The concentration of the ions
The nature of the electrode
• Usually, inert electrodes such as graphite or Pt are used for electrolysis. They simply act as a point of connection
b/w the electrical circuit and the solution and they are not interfering with the reaction.
The applied voltage
• It should be optimum for the reaction. If it is increased/decreased the electrolysis and the separation will not be of
accurate.

Water electrolysis is the best way to produce hydrogen without polluting. Nevertheless when fossil fuels are used as the
primary source of electricity, the problem of environmental pollution remains unsolved. Therefore, electricity provided from
renewable energy sources is essential for the production of emission-free hydrogen, since: (i) water on earth is abundant (ii)
hydrogen is provided from abundant renewable energy sources (iii) hydrogen oxidation for the production of electrical
energy (in fuel cells) only produces water, which can be recycled.
Pure water—low conductivity, some salts such as sulphates or electrocatalysts are added..

Driving cars using water?

alkaline fuel cellThe hydrogen produced by electrolysis may be used as a fuel in a fuel cell (see right) but the efficiency of
the overall process (synthesis of H2 from H2O followed by oxidation of H2 to H2O) is always well below 100%. Thus the
hydrogen produced can never be used to drive the electrolysis that produces it [2689]. This fact is governed by the
unbreakable laws of thermodynamics but often seems to be ignored by people proposing cars that run on 'water' or 'Brown's
gas' (a mixture of H2 and O2 produced by electrolysis [1879]). Generating hydrogen by electrolysis is only (optimally) about
60% efficient and the use of this hydrogen in a car is (optimally) also only about 60% efficient, so two thirds of the energy
required is wasted. The only time excess energy may apparently be produced (on a laboratory scale) is when the electrodes
themselves react; a important factor that produces artifacts when using some stainless steel electrodes but often ignored.