The Manufacture of Sulfuric Acid

Introduction

It was once said that a country's wealth could be measured by its production
of sulfuric acid (H2SO4). That may no longer be true, but the acid is still used in
the manufacture of paints, fertilizers, plastics, fabrics, dyes, detergents, and
many other useful products. In this unit you can find out how we make the
acid in industry.
The Contact process
The most important process for making sulfuric acid in industry is the Contact
process. We can think of the Contact process as involving three stages. Look
at the process shown in Fig.1 below:

Figure 1. The Contact process.

Stage 1

Sulfur is imported from Poland or the USA. We can also obtain sulfur from the
impurities in fossil fuels such as coal. In the first stage of the process, sulfur is
burned in air to make sulfur dioxide gas:

sulfur + oxygen sulfur dioxide

S(l) + O2(g) SO2(g)
Stage 2

In the next stage, we convert the sulfur dioxide to sulfur trioxide:

sulfur dioxide + oxygen sulfur trioxide

2 SO2(g) + O2(g) 2 SO3(g)

The reaction happens on a catalyst of vanadium(V) oxide to speed up the

reaction. As much sulfur dioxide as possible is changed into sulfur trioxide,
and releases of sulfur dioxide are prevented because it is a gas that causes
acid rain.

Stage 3

In the final stage, the sulfur trioxide is converted into sulfuric acid. The sulfur
trioxide gas is absorbed into very concentrated sulfuric acid (a 98 per cent
solution of H2SO4in water), producing a thick fuming liquid called oleum. The
oleum is mixed carefully with water, and the sulfur trioxide in the oleum reacts
with the water as follows:

sulfur trioxide + water sulfuric acid

SO3(g) + H2O(l) H2SO4(l)

You may wonder why the sulfur trioxide is not mixed directly with pure water.
The problem is that this is a highly
exothermic reaction, which would produce a fine mist of sulfuric acid that is
difficult to condense and could escape to pollute the air.

Conditions in the Contact process

Look at the reversible reaction in which sulfur dioxide is converted into sulfur
trioxide: 2 SO2(g) + O2(g) 2 SO3(g) ΔH = −197 kJ/mol

The forward reaction is exothermic (gives out heat), so the formation of sulfur
trioxide will be favoured by low temperatures. However, the vanadium(V)
oxide catalyst will not work below 400 °C, so the reaction is conducted at 450
°C to increase the rate of reaction. You still get an excellent yield of sulfur
trioxide (97 per cent) at this temperature, and at a reasonable rate with the
help of the catalyst.

The forward reaction is also favoured by high pressures. But with a yield of
about 95 per cent anyway, it's not worth spending more money to compress
the reacting gases. The pressure used is just enough to move the gases
through the plant.

Summary

Sulfuric acid is manufactured in the Contact process.

First, sulfur is burned in air to give sulfur dioxide.

Then sulfur dioxide is mixed with more air to yield sulfur trioxide in a reversible
reaction.

A compromise temperature of 450 °C is chosen to speed up the reaction. The

gases pass through layers of vanadium(V) oxide catalyst which also increase
the rate of reaction.

Finally, sulfur trioxide is mixed with a mixture of 98 per cent solution of sulfuric
acid to form an even more concentrated form of sulfuric acid (99.5 per cent).
Question:
Which step in the Contact process involves a reversible reaction?

Burning sulfur
Changing sulfur dioxide into sulfur trioxide
Changing sulfur trioxide into sulfuric acid

Why are there strict limitations set on the release of sulfur dioxide gas into the air as a
waste
product from the process?

It causes global warming.

It causes acid rain.

Decide whether the following statements about the conversion of sulfur dioxide
to sulfur trioxide are true or false.
You get a higher yield of sulfur trioxide at
equilibrium with a low temperature.

You get a higher yield of sulfur trioxide at

equilibrium with a high temperature.

You get a higher yield of sulfur trioxide at

equilibrium with a low pressure.

You get a higher yield of sulfur trioxide at

equilibrium with a high pressure.

1. What is the formula of sulfuric acid?

HSO3
HSO4
H2SO4
H2S
2. Which
element is burned in the first stage of the manufacture of sulfuric acid?

Hydrogen
Sulfur
Vanadium

3. What is the name of the catalyst used in the Contact process?

Iron
Iron(III) oxide
Vanadium(V) oxide

4. What temperature is chosen for the Contact process?

150 °C
250 °C
350 °C
450 °C
550 °C

5. Insert the same number in both boxes to balance the equation below.

SO2(g) + O2(g) SO3(g)

6. In the Contact process, the final stage involves dissolving the sulfur trioxide in …

pure water.
98 per cent sulfuric acid solution.
vanadium(V) oxide.

7. Does the catalyst used in the Contact process increase the percentage of sulfur
 trioxide formed?

Yes
No

8. Explain the temperature used in the Contact process.

The Manufacture of Nitric Acid and Ammonium Nitrate

Introduction

Nitric acid (HNO3) is used in the manufacture of paints, fertilizers, plastics,

fabrics, dyes, detergents, and explosives. In this unit you can find out how the
acid is made in industry and how it is used in the production of ammonium
nitrate fertilizer.
Making nitric acid
The first stage in the industrial manufacture of nitric
acid uses ammonia from the Haber process (see the unit The Manufacture of
Ammonia). The ammonia is oxidized by the oxygen in air. This is a reversible
reaction, achieved using a platinum/rhodium catalyst. The
catalyst consists of a gauze of the precious metals through which the gases
pass.

ammonia + oxygen nitrogen monoxide + water (steam)

4 NH3(g) + 5 O2(g) 4 NO(g) + 6 H2O(g) ΔH = −910 kJ/mol

The forward reaction is strongly

exothermic and the temperature on the surface of the catalyst rises to about
900 °C. Some of this energy given out is used to heat up the incoming gases
– so it is useful, even though high temperatures favour the reverse reaction.

Look at the whole process shown in Fig.1 below:

Notice that in the second stage of the process the gases are cooled:

nitrogen monoxide + oxygen nitrogen dioxide

2 NO(g) + O2(g) 2 NO2(g) ΔH = −115 kJ/mol

This favours the formation of nitrogen dioxide, which goes on to make the
nitric acid:

nitrogen dioxide + oxygen + water nitric acid

4 NO2(g) + O2(g) + 2 H2O(l) 4 HNO3(l)

Making ammonium nitrate

Much of the nitric acid made in industry is used to make the fertilizer,
ammonium nitrate (NH4NO3).

Ammonia is an alkali, so it will undergo a neutralization reaction with nitric

acid. The salt made is ammonium nitrate:

ammonia + nitric acid ammonium nitrate

NH3(aq) + HNO3(aq) NH4NO3(aq)

Look at the process to manufacture ammonium nitrate shown in Fig.2 below:

Notice that the ammonium nitrate is produced in the form of solid pellets to
make it easier to spread on fields.
Summary

Ammonia from the Haber process is used to manufacture nitric acid.

The ammonia is oxidized by oxygen in air in the first stage of the process to
make nitric acid. The reaction takes place on a platinum/rhodium catalyst:

ammonia + oxygen nitrogen monoxide + water (steam)

The gases are cooled, and nitrogen oxide is then further oxidized to form
nitrogen dioxide:

nitrogen monoxide + oxygen nitrogen dioxide

Finally, the nitrogen dioxide is mixed with more air plus water to form the nitric
acid:

nitrogen dioxide + oxygen + water nitric acid

Nitric acid and ammonia react to form the important fertilizer, ammonium
nitrate, in a neutralization reaction:

ammonia + nitric acid ammonium nitrate

Question:
Which substance is oxidized in the first stage of the process to make nitric acid?

Oxygen
Nitrogen monoxide
Ammonia

Name the catalyst used in the manufacture of nitric acid.

Iron/vanadium
Platinum/rhodium
Nickel/silver

Look at this reaction: 2 NO(g) + O2(g) 2 NO2(g)

Increasing the pressure would favour the formation of which gas?

Nitrogen monoxide
Nitrogen dioxide
1. Match the formula to the correct
compound:
NH3

HNO3

NH4NO3

NO2

2. Which precious metals are used to catalyse the

oxidation of ammonia when making nitric acid?
Gold

Silver

Platinum

Rhodium

3. Insert the same number in both boxes to balance the equation below.
 NO2(g) + O2(g) + 2H2O(l) HNO3(l)

4. What type of substance is ammonia?

An acid
A base

5. Name the salt formed when ammonia solution reacts with nitric acid.

6. What is the major use of the compound in the previous question?