CHEMISTRY MASTER GUIDE 5 BY KIMUTAI SONOIYA

INDUSTRIAL PROCESSES REVISION KIT 1

1. HABER PROCESS
Large Scale Manufacture of Ammonia, the Haber Process
Ammonia is prepared on a large scale by the Haber Process.
The raw materials
Nitrogen- obtained by the fractional distillation of liquid air.
Hydrogen - obtained from natural gas or as a by-product of cracking long chain alkanes.
The process
Nitrogen and hydrogen gases are mixed in the ratio of 1:3 and passed through a purifier
to remove impurities which would otherwise poison the catalyst. The impurities removed
are; carbon(IV) oxide, sulphur(IV) oxide and dust particles.
The mixture of nitrogen and hydrogen is then compressed to between 200 and 500
atmospheres and passed into a catalytic chamber maintained at temperatures of
between 400°C and 500°C. Iron is used as the catalyst. The reaction is highly exothermic
and sustains the temperature in the catalytic chamber.
N2(g) + 3H2(g) 2NH3(g) + Heat
The hot mixture of ammonia and gases which have not reacted are passed into the heat
exchanger where cooling takes place. The heat is used to heat the incoming mixture of
nitrogen and hydrogen; this makes the process economical.
The ammonia produced is liquefied in the condenser and stored in cylinders. The gases
which have not reacted are recycled therefore reducing wastage.

The yield of ammonia is high at higher pressures and low temperature. However, it is
expensive to maintain higher pressure. At low temperatures the reaction is slow.
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To reduce the production cost optimum conditions of 500°C, 200 atmospheres and iron
catalyst are employed.

Uses of Ammonia
• As a fertiliser.
• Manufacture of nitrogenous fertilisers.
• As a refrigerant, e.g., in large scale refrigerating plants such as ships and
warehouses.
• Softening water.
• Removal of greasy stains.
• Manufacture of hydrazine that is used as rocket fuel.

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2. OSTWALD PROCESS
Industrial Manufacture of Nitric(V) Acid (Ostwald process)
Nitric(V) acid is manufactured by a process that relies on the catalytic oxidation of
ammonia.

The raw materials for this process are ammonia, air and water.

A mixture of ammonia and air is first purified to remove dust particles and other impurities
that would otherwise ‘poison’ the catalyst.
The mixture is then compressed to a pressure of 9 atmospheres and passed on to the
catalytic chamber via the heat exchanger.
As it passes through the heat exchanger, the temperature of the ammonia-air mixture
rises to 230°C.
In the catalytic chamber, the temperature of the mixture is raised further to 900°C. It is
then passed over a platinum-rhodium catalyst. The ammonia combines with oxygen to
form nitrogen(II) oxide. The reaction is highly exothermic.
4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)
The hot gaseous products from the catalytic chamber are cooled in the heat exchanger.
Nitrogen(II) oxide is mixed with more air and is oxidised to nitrogen(IV) oxide.
2NO(g) + O2(g) 2NO2(g)
This reaction is carried out at a temperature of below 45°C to ensure a high yield of
nitrogen(IV) oxide.
The mixture of nitrogen(IV) oxide, air and unreacted nitrogen(II) oxide is passed up the
absorption tower against a downward flow of hot water. Nitrogen(IV) oxide and water
combine to form nitric(V) acid and nitric(III) acid (nitrous acid).
2NO2 (g) + H2O (l) → 2HNO3(aq) + 2HNO2(g)
Nitric (V) acid Nitric (III) acid
The nitric(III) acid formed is oxidised to nitric(V) acid by excess air.
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2HNO2(g) + O2 (g) → 2HNO3(aq)

Nitric (III) acid Nitric (V) acid

The mixture that results is 65% nitric(V) acid and 35% water.

A more concentrated acid may be obtained by careful distillation of the solution over
phosphorus(V) oxide or concentrated sulphuric(VI) acid that acts as a dehydrating
agent.
Concentrated nitric(V) acid is a colourless fuming liquid with a boiling point of 83°C.
Commercial nitric(V) acid is 68% pure and has a density of 1.42 g/cm3.

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3. FRASCH PROCESS
Extraction Of Sulphur: The Frasch process
The Frasch process is employed in the extraction of Sulphur. The process is based on the
low melting point of sulphur which ranges between 113 °C and 119°C. In the Frasch
process, three concentric pipes of different diameters 2 cm, 8 cm, and 15 cm are sunk
into the sulphur deposits underground.

Water is heated to about 170°C under pressure of about 10 atmospheres and is forced
down the outermost pipe. The pressure ensures that the water remains in liquid state at
such high temperature.
Hot air at a pressure of 15 atmospheres is forced down the innermost pipe. This produces
a light froth consisting of a mixture of molten sulphur and water. The high pressure forces
the mixture up the middle pipe.
The mixture is run into large tanks on the surface where the sulphur solidifies at 115°C,
Separates from the water and is stored. Sulphur obtained this way in usually over 99%
pure.

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4. CONTACT PROCESS
Large Scale Manufacture of Sulphuric(VI) Acid
Sulphuric(IV) acid is manufactured by the contact process shown below.

The raw materials for its manufacture are sulphur(IV) oxide and air.
Sulphides or sulphur are burnt in air to produce sulphur(IV) oxide.
 Burning of sulphur is the most convenient method of producing sulphur(IV) oxide.
S(s) + O2(g) SO2(g)
The sulphur(IV) oxide contains dust particles as impurities.
 The impurities reduce the surface area of the catalyst, thus impairing its efficiency.
These impurities are said to poison the catalyst.
 The dust impurities are removed by electrostatic precipitation.
The mixture of gases is passed through concentrated sulphuric(VI) acid in order to dry it.
After purification, the gaseous mixture is pre-heated in the heat exchanger to attain
suitable reaction temperature before being passed into the catalytic chamber.
In the catalytic chamber, sulphur(IV) oxide and oxygen react to form sulphur(VI)
oxide.

Either platinum or vanadium(V) oxide may be used as catalyst.

 However, the vanadium(V) oxide(V2O5) is preferred because it is cheaper and

less easily poisoned.
For maximum yield of sulphur(VI) oxide in the contact process, low temperature and high
pressure are necessary.
 However, at low temperature the reaction is slow while high pressure is expensive
to maintain. A temperature of 450°C and pressure of 2 to 3 atmospheres are used
and are referred to as optimum conditions.

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The sulphur(VI) oxide is not dissolved directly in water because the excessive heat
generated could boil the acid to produce a mist of fine droplets of sulphuric(VI) acid in
air. Hence, the gas is dissolved in concentrated sulphuric(VI) acid to form oleum (H 2S2O7).

 Sulphuric(VI) acid is obtained by diluting oleum with water.

H2S2O7(1) + H2O(l) 2H2SO4(l)
During the contact process, not all the sulphur(IV) oxide is converted into sulphur (VI)
oxide: only 98% conversion of sulphur(IV) oxide to sulphur(VI) oxide occurs.
 Sulphur(IV) oxide is a pollutant, passing the exhaust gases through chimneys lined
with calcium hydroxide reduces the amount of sulphur(IV) oxide released to the
atmosphere. This is referred to as scrubbing the gas.
Ca(OH)2(aq) + SO2(g) CaSO3(s) + H2O(l)
In some industries, filters fitted with strong alkalis are installed to remove any traces of
acid or mist from exhaust gases.

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5. SOLVAY PROCESS
In places where trona is not available, sodium carbonate and sodium hydrogen carbonate are
manufactured by the Solvay process.
1. Raw Materials
 Brine (Concentrated sodium chloride) is obtained from sea salt by evaporating
the water to obtain crystals from salty seas/lakes.
 Ammonia gas is obtained from the Haber Process.
 Limestone (calcium carbonate) from chalk /limestone rich rocks.
The best site for the Solvay process plant should be close to a river or large source of
water to cool down the carbonator.

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The Chemical Processes

(i) Ammonia is dissolved in brine in the Solvay tower to produce ammoniacal brine.
A lot of heat is produced in the process. The amount of heat produced is
controlled by regulating the flow of brine into the Solvay tower.
(ii) The ammoniacal brine is then pumped into the carbonator from the top where it
trickles down the carbonator while carbon (IV) oxide is pumped from the base.
Sodium hydrogen carbonate and ammonium chloride are formed from the
reactions that occur.
The reactions that take place in the carbonator are:
NH3(g) + CO2(g) + H2O(l) → NH4HCO3(aq)
NH4HCO3(aq) + NaCl(aq) → NaHCO3(s) + NHCl4(aq)
The reactions can be summarized as:
NH3(g) + CO2(g) + NaCl(aq) + H2O(l) → NaHCO3(s) + NH4Cl(aq)
Sodium hydrogen carbonate being less soluble than ammonium chloride at low
temperatures, forms crystals in the lower cooled part of the carbonator.
 The carbonator has to be cooled regularly to reduce the amount of heat
produced in it.
 The carbon (IV) oxide for this step is obtained from thermal decomposition of
calcium carbonate and roasting of coke in the lime kiln.
heat
CaCO3(s) → CaO(s) + CO2(g) (thermal decomposition)
C(s) + O2(g) → CO2(g) (roasting)
(iii) Sodium hydrogen carbonate is separated from ammonium chloride by filtration.
The solid sodium hydrogen carbonate forms the residue while the soluble
ammonium chloride forms the filtrate.

(iv) Sodium hydrogen carbonate is dried and decomposed by heat at 300ºC to

produce sodium carbonate.
heat
NaHCO3(s) → Na2CO3(s) + CO2(g) + H2O(l)
The carbon (IV)oxide gas and water are recycled to the carbonator.

(v) The calcium oxide produced in the limestone kiln is slaked (combined) with water
in the slaker to form calcium hydroxide.

CaO(s) + H2O(l) → Ca(OH)2(s)

The calcium hydroxide formed is then mixed with the filtrate ammonium chloride
in the distiller (ammonia regenerator) to produce ammonia gas, water and
calcium chloride.
Ca(OH)2(s) + 2NH4Cl(aq) → CaCl2(s) + 2H2O(l) + 2NH3(g)

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Ammonia gas is recycled back to the ammoniacal brine chamber and water to
the slaker.
2. Efficiency and Products of the process.
(i) The Solvay process is one of the best examples of an efficient industrial chemical
process, because:
 Pollution problems are considerably reduced. The carbon (IV) oxide and
ammonia gases produced are recycled to minimise costs.
 The water produced is also recycled to minimise thermal effects on the water
source near the plant.
 The process does not involve large consumption of energy because the coke
burned in the kiln supplies the necessary heat in the process.

(ii) The products in the Solvay process have several uses.

Calcium chloride is the only by-product in the process and may be used:
(a) As drying agent in the school laboratory during gas preparation (except
ammonia gas)
(b) To lower the melting point of solid sodium chloride / rock salt salts during the
Downs process for industrial extraction of sodium metal.
(c) As a food additive and a food preservative
(d) Used for de-icing roads in winter

Sodium carbonate is used:

(a) During making glass. It is used to lower the melting point of the mixture of
sand/SiO2 from 1650oC and CaO from 2500oC to around 1500oC
(b) In softening hard water
(c) In the manufacture of soapless detergents.
(d) Swimming pool “pH increaser”.
(e) In the paper industry
(f) Used in making of sodium silicate. The sodium silicate is used in the making of
detergents.

Sodium hydrogen carbonate itself can be used:

(a) As baking powder and preservation of some soft drinks.
(b) As a buffer agent and antacid in animal feeds to improve fibre digestion.
(c)Making dry chemical fire extinguishers.

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6. THE MERCURY CELL

Manufacture of Sodium Hydroxide and Chlorine from Electrolysis of Concentrated Sodium
Chloride (Brine)
Sodium hydroxide and
chlorine are
manufactured by the
electrolysis of brine by
use of mercury cell,
shown alongside.

The electrolyte in the mercury cell is a concentrated solution of sodium chloride (Brine).
The anode in the cell is made of carbon or titanium because they do not react with
chlorine gas. While the cathode is a moving film of mercury.

When an electric current is passed through concentrated sodium chloride solution,

chloride (Cl–) ions and hydroxide (OH–) ions migrate to the anode. Chloride ions are
preferentially discharged because of their relatively high concentration.

2Cl–(aq) 2Cl(g) + 2e–

2Cl(g) Cl2(g)
Both sodium (Na+) ions and hydrogen (H+) ions migrate to the cathode (moving film of
mercury). Hydrogen ions are not discharged because of the over-potential (excess
power) required to discharge it. Sodium ions are preferentially discharged instead.

2Na+(aq) + 2e– 2Na(l)

The sodium atoms formed dissolve in the hot mercury to form sodium amalgam (Na
Hg)

Na(l) + Hg(l) NaHg(l)

The sodium amalgam is passed through a trough in the cell that contains distilled water.
The sodium in the amalgam then reacts with water to form a solution of sodium hydroxide
and hydrogen gas. Hydrogen is pumped out to the required place, while mercury is
regenerated and recycled.

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2NaHg(l) + 2H2O(l) 2NaOH(aq) + 2Hg(l) + H2(g)

The sodium hydroxide obtained this way is about fifty per cent pure. Pure sodium
hydroxide is obtained by evaporating the water in the aqueous sodium hydroxide
solution to get pellets or flakes.
The process is expensive due to the high cost of mercury and the safety measures
applied since mercury is poisonous.

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