Unit 2 mod 3 chlorine production & Contact Process

Mar 6 2010 page 1 of 4

CHLORINE PRODUCTION
In diaphragm cell electrolysis, an asbestos (or polymer-fiber) diaphragm
separates a cathode and an anode, preventing the chlorine forming at the
anode from re-mixing with the sodium hydroxide and the hydrogen
formed at the cathode.
The salt solution (brine) is continuously fed to the anode compartment
and flows through the diaphragm to the cathode compartment, where the
caustic alkali is produced and the brine is partially depleted.
As a result, diaphragm methods produce alkali that is quite dilute (about
12%) and of lower purity than do mercury cell methods. But diaphragm
cells are not burdened with the problem of preventing mercury discharge
into the environment. They also operate at a lower voltage, resulting in
an energy savings over the mercury cell method, but large amounts of
steam are required if the caustic has to be evaporated to the commercial
concentration of 50%.

Economic advantages
1. Less energy used because it operates at a lower voltage
2. No risk of releasing mercury into environment (i.e. less cost
involved in expensive recovery methods)

Unit 2 mod 3 chlorine production & Contact Process

Mar 6 2010 page 2 of 4

Economic disadvantages
Very dilute sodium hydroxide produced (12%) and industry requires
50%. Large amounts of steam is required to concentrate the alkali.
The chlorine produced is usually not very pure and requires purification
Chlorine can also be produced via the flowing mercury cathode cell
The cathode is a thin layer of mercury and graphite is the anode.
The electrode reactions are:At cathode Na+ + e- Na
At anode 2Cl- -2e- Cl2
However the sodium undergoes further reactions
a) Na + Hg Na/Hg
b) 2Na/Hg + 2H2O 2NaOH + H2 + 2Hg
The product is chlorine and by-products are sodium hydroxide and
hydrogen gas.
Importance of halogens and their compounds
These substances are used in the manufacture of:1. Bleaches
2. PVC
3. Solvents
4. Aerosols
5. Refrigerants 6. Anaesthetics
7. Purification of drinking water supplies 8. Herbicides/fungicides
Practice Question

Unit 2 mod 3 chlorine production & Contact Process Mar 6 2010 page 3 of 4
What is the ratio of moles of NaCl used to moles of Cl2 produced?
Use this ratio to determine mass of NaCl in kg required to produce 2.5 x 1010 kg
of Cl2

CONTACT PROCESS
The process can be divided into three stages:
1. Preparation and purification of sulphur dioxide
2. Catalytic oxidation (using vanadium pentoxide catalyst) of sulphur
dioxide to sulphur trioxide
3. Conversion of sulphur trioxide to sulphuric acid
Purification of air and SO2 (using an electrostatic precipitator) is necessary to
avoid catalyst poisoning (i.e. removing catalytic activities). The gas is then
washed with water and dried by sulphuric acid.
To conserve energy, the mixture is heated by exhaust gases from the catalytic
converter by heat exchangers.
Sulphur dioxide and oxygen then react in the manner as follows:
2 SO2(g) + O2(g) 2 SO3(g) : H = 197 kJ mol1
To increase the reaction rate, high temperatures (450 C), medium pressures (1-2
atm), and vanadium(V) oxide (V2O5) are used to ensure a 96% conversion.
Hot sulfur trioxide passes through the heat exchanger and is dissolved in
concentrated H2SO4 in the absorption tower to form oleum:
H2SO4(l) + SO3(g) H2S2O7(l)
Note that directly dissolving SO3 in water is impractical due to the highly
exothermic nature of the reaction. Acidic vapour or mists are formed instead of a
liquid.
Oleum is reacted with water to form concentrated H2SO4.
The average percentage yield of this reaction is around 30%.
H2S2O7(l) + H2O(l) 2 H2SO4(l)

Unit 2 mod 3 chlorine production & Contact Process

Mar 6 2010 page 4 of 4

Importance of compounds of sulphur in industry

1. SO2
Used as a food preservative in juices and jams. It creates an acidic and
oxidising medium which prevents the growth of any microbes.
2. Sulphuric acid
Used in the manufacture of fertilisers, manufacture of detergents, production
of phosphoric acid, used to help manufacture fabrics e.g. nylon, in petroleum
refining, to manufacture dyes and as the battery acid in car batteries.

Impact on the environment

Emissions of SO2 causes drastic changes in the atmosphere. It plays a major
role in the formation of acid rain via the reaction
SO2 + H2O H2SO3 or even 2SO2 + O2 + 2H2O 2H2SO4
Acid rain damages or destroys buildings and vegetation and of course it is not
healthy for the aquatic life as it reduces the pH of the water decreasing their
quality of life. It also can cause the mobilisation of toxic ions in the soil which
results in vegetations growth being affected.
SO2 emissions can cause respiratory problems as it is irritating and causes
wheezing and shortness of breath.

Practice Questions