MANUFACTURING CHLORINE USING A

DIAPHRAGM AND A MEMBRANE CELL

This page describes the manufacture of chlorine by the

electrolysis of sodium chloride solution using a diaphragm cell
and a membrane cell. Both cells rely on the same underlying
chemistry, but differ in detail. For UK A level (or equivalent)
purposes, you will only need to know details of one of these
cells. Read the background chemistry section below, and then
concentrate on the cell you need to know about.

Background chemistry

Chlorine is manufactured by electrolysing sodium chloride

solution. In fact, the electrolysis of sodium chloride solution can
be used to make three useful substances - chlorine, sodium
hydroxide and hydrogen.

The chemistry of the electrolysis process

Sodium chloride solution contains:

sodium ions,

chloride ions,

hydrogen ions (from the water),

hydroxide ions (from the water).

The hydrogen and hydroxide ions come from the equilibrium:

Note: Strictly speaking, this is a simplification. The H+(aq)

ions could be better shown as hydroxonium ions, H3O+. That
would need two water molecules on the left-hand side of the
equilibrium. The simplification is fine for this topic.

At any one time, the concentration of hydrogen ions or

hydroxide ions will be very small - the position of equilibrium lies
well to the left-hand side.


At the anode

The negative ions, chloride and hydroxide, get attracted towards

the positively charged anode. It is actually easier to liberate
hydroxide ions (to give oxygen) than chloride ions (to give
chlorine), but there are far, far more chloride ions arriving at the
anode than hydroxide ions.

The major reaction at the anode is therefore:

Two chloride ions each give up an electron to the anode, and

the atoms produced combine to give chlorine gas.

The chlorine is, however, contaminated with small amounts of

oxygen because of a reaction involving hydroxide ions giving up
electrons as well.

The chlorine has to be purified to remove this oxygen.

At the cathode

Sodium ions and hydrogen ions (from the water) are attracted to
the negative cathode. It is much easier for a hydrogen ion to
pick up an electron than for a sodium ion. So this reaction
happens:

As the hydrogen ions are converted into hydrogen gas, the

water equilibrium tips to the right to replace them.

The net effect of this is that there is a build up of sodium ions

and these newly-produced hydroxide ions around the cathode.
In other words, sodium hydroxide solution is being formed
around the cathode.

The need to keep all the products separate

If chlorine comes into contact with hydrogen, it produces a
mixture which will explode violently on exposure to sunlight or
heat. Hydrogen chloride gas would be produced. Obviously, the
two gases need to be kept apart.

However, chlorine also reacts with sodium hydroxide solution to

produce a mixture of sodium chloride and sodium chlorate(I) -
also known as sodium hypochlorite. This mixture is commonly
sold as bleach.

Therefore, if you are trying to manufacture chlorine and sodium

hydroxide rather than bleach, you have to keep the chlorine and
sodium hydroxide apart as well.

The diaphragm and membrane cells are designed so that all the
products are kept separate.

The diaphragm cell

Note: This is a simplification of a real cell. For example, in a

real diaphragm cell, the electrodes are not a single block of
metal. If you are interested, you can find pictures and
descriptions of real electrodes by doing a Google search on
diaphragm cell and looking for manufacturers' websites.

The diaphragm

The diaphragm is made of a porous mixture of asbestos and

polymers. The solution can seep through it from the anode
compartment into the cathode side.

Notice that there is a higher level of liquid on the anode side.

That makes sure that the flow of liquid is always from left to right
- preventing any of the sodium hydroxide solution formed finding
its way back to where chlorine is being produced.

Production of the chlorine

Chlorine is produced at the titanium anode according to the

equation:

It is contaminated with some oxygen because of the reaction:

The chlorine is purified by liquifying it under pressure. The

oxygen stays as a gas when it is compressed at ordinary
temperatures.

Production of the hydrogen

The hydrogen is produced at the steel cathode:

Production of the sodium hydroxide

A dilute solution of sodium hydroxide solution is also produced

at the cathode (see above for the explanation of what happens
at the cathode). It is highly contaminated with unchanged
sodium chloride solution.

The sodium hydroxide solution leaving the cell is concentrated

by evaporation. During this process, most of the sodium chloride
crystallises out as solid salt. The salt can be separated,
dissolved in water, and passed through the cell again.

Even after concentration, the sodium hydroxide will still contain a

small percentage of sodium chloride.

The membrane cell

 Note: This is a simplification of a real cell to show the main
features. You will find other diagrams with the inlets and
outlets in different places or in more detail. This isn't
something you need to worry about at this level.

The membrane

The membrane is made from a polymer which only allows

positive ions to pass through it. That means that the only the
sodium ions from the sodium chloride solution can pass through
the membrane - and not the chloride ions.

The advantage of this is that the sodium hydroxide solution

being formed in the right-hand compartment never gets
contaminated with any sodium chloride solution.

The sodium chloride solution being used has to be pure. If it

contained any other metal ions, these would also pass through
the membrane and so contaminate the sodium hydroxide
solution.

Production of the chlorine

Chlorine is produced at the titanium anode according to the

equation:

It is contaminated with some oxygen because of the reaction:

The chlorine is purified by liquifying it under pressure. The
oxygen stays as a gas when it is compressed at ordinary
temperatures.

Production of the hydrogen

The hydrogen is produced at the nickel cathode:

Production of the sodium hydroxide

An approximately 30% solution of sodium hydroxide solution is

also produced at the cathode (see above - in the background
chemistry section - for the explanation of what happens at the
cathode).

Questions to test your understanding

If this is the first set of questions you have done, please read the
introductory page before you start. You will need to use the BACK BUTTON
on your browser to come back here afterwards.

questions on the manufacture of chlorine

answers

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Jim Clark 2007 (modified June 2015)