13.

0 NITROGEN AND
SULPHUR COMPOUNDS
SULPHUR
OBJECTIVES

By the end of the subtopic, you should be able to:

• Explain the manufacture of sulphuric acid by the Contact process in terms of
the principles of kinetics and equilibria.
• Recognise the industrial importance of sulphuric acid.
• Recognise the environmental consequences of compounds of Sulphur.
• Describe the use of sulphur dioxide in food preservation.
• Preparing ammonium sulphate in the laboratory.
INTRODUCTION
• Contact process, is a modern industrial method of producing sulphuric acid.
• Sulphur dioxide and oxygen, passed over a hot catalyst, react to form sulphur
trioxide, which in turn reacts with water to make sulphuric acid.
• In Zimbabwe, Sulphuric acid is produced in Harare at Zimbabwe phosphate
industries; (Zimphos) a company that produces Sulphur based fertilisers.
• Raw materials for the contact process are Sulphur dioxide, oxygen and water.
• Sulphur dioxide is produced from iron pyrites which are roasted to SO2
• Iron pyrites are mined at Iron Duke is a mine located in Mashonaland Central
Province of Zimbabwe.
• Conditions of the Contact Process are:
• Temperature 4500C
• Pressure of 1atm
• Catalyst Vanadium (V) Oxide
 Fig 13.2.1: Showing Contact process plant at Zimphos.
Contact Process
• The Contact process occurs in 4 steps which are:
Step 1: The oxidation of sulphur to SO2.
Step 2: Catalytic oxidation of SO2to SO3.
Step 3: Absorption of SO3by impure H2SO4to produce oleum (H2S2O7).
Step 4: Dilution of oleum with water, to produce ≈pure H2SO4.
Stage 1: Oxidation of Sulphur
2𝐹𝑒𝑆2 (𝑠) + 4𝑂2 (𝑔) → 𝐹𝑒2 𝑆𝑂2 (𝑠) + 3𝑆𝑂2 (𝑔)
• This reaction occurs in a burner, and is classified as a combustion reaction, since
large amounts of heat are evolved.
• The sulphur dioxide produced is then purified to remove moisture and dust, and
any substances which may poison or interfere with the function of the catalyst in
the next stage.

Step 2: Catalytic oxidation of SO2 to SO3

2𝑆𝑂2 (𝑔)+𝑂2 𝑔 ⇋ 2𝑆𝑂3 (𝑔)∆H= -197 kJ/mol
• Sulphur dioxide gas is oxidised to sulphur trioxide by oxygen, using vanadium (V)
oxide (V2O5 ) as a catalyst.
• This reaction occurs in a vessel referred to as a converter.
• To maximize yields certain physical conditions should be considered such as:
Temperature
• Equilibrium considerations
• Since the forward reaction is exothermic, at higher temperatures the backward
reaction is favoured which is the dissociation of SO3.
• At very low temperature, the rate of reaction of SO2 and O2 is very slow and at
an optimum temperature of about 4500C, the rate of formation of SO3 is high
and rate of decomposition of SO3 is at its minimum.
• According to Le Chatelier's Principle, the temperature range which best meets
kinetics and thermodynamics requirements for high yield in the synthesis of SO3 is
located in between 4000C to 5000C, with optimum temperature at about 4500C.
• Rate considerations
• The lower the temperature, the slower the reaction becomes, and likewise the
increase in temperature increase the rate of reaction.
• Increase in temperature increases the rate of collisions thus increase the rate of
formation of products
• The compromise: 400 - 450°C is a compromise temperature producing a fairly
high proportion of sulphur trioxide in the equilibrium mixture.
Pressure
• Equilibrium considerations
• According to Le Chatelier's Principle, increase in pressure of a gaseous system, the system
will respond by favouring the reaction which produces fewer molecules as that will cause
the pressure to fall again.
• In the forward reaction which formation of sulphur trioxide, has the number of moles of
gaseous components is decreasing. High pressures also increase the rate of the reaction.
• The equilibrium constant in terms of partial pressure is given by
𝑃(𝑆𝑂3 )2
𝐾𝑝 =
𝑃(𝑆𝑂3 )2 𝑃(𝑂2 )
• Increase in pressure increases the formation of SO3 and is indicated by a high Kp
• Rate considerations
• Increasing the pressure of any gaseous system brings the gaseous molecules closer
together.
• Increasing the pressure of a gaseous system also increases the kinetic energies of the
gaseous molecules thereby increasing their chances of collision between themselves, the
walls of the container at the surface of the catalyst.
• Compromise Conditions
• A gas pressure between 100 and 200 kPa is used to increases the collision
frequency between the reacting gases. The increase in yield by driving the
reaction to the right. These pressures are also sufficiently low to avoid
expensive apparatuses.
• An excess of oxygen will drive the reaction to the product side, increasing
the yield. Thus, a 5:1 air: SO2 ratio is used (essentially 1:1 O2:SO2) creating an
excess of oxygen.
• A catalyst is used to increase the rate of reaction, compensating for the
lower temperature. Its identity is V2O5 supported on a silica bed.
• Step 3: Absorption of SO3by impure H2SO4 to produce oleum H2S2O7
• Sulphur trioxide is mixed with concentrated sulphuric acid in an absorption
tower.
𝐻2 𝑆𝑂4 (𝑙) + 𝑆𝑂3 (𝑔) → 𝐻2 𝑆2 𝑂7 (𝑙)
• The SO3 formed instep 2 is passed into the base of the absorption tower, and
concentrated H2SO4 is applied at the top of the tower. The rising SO3 and
H2SO4 react, to form oleum H2S2O7.
• To maximise conversion of SO2 and hence minimise emissions of this gas into
the atmosphere, most plants now employ the “double absorption” process.
• In this process, unreacted gases in the absorption tower are recycled to the
converter for one or two additional passes over the catalyst beds, and then
returned to the absorption tower.
Step 4: Dilution of oleum with water, to produce ≈ pure H2SO4
• The oleum is reacted with water to form > 98% pure H2SO4
• 𝐻2 𝑆2 𝑂4 (l)+ 𝐻2 𝑂(𝑙) → 2𝐻2 𝑆𝑂4 (l)
• Since SO3 cannot directly react with H2O to produce H2SO4.
• As this reaction is highly exothermic, a net back reaction is favoured,
reducing the yields of sulphuric acid.
• Furthermore, at higher temperatures, the acid forms a mist which is difficult
and expensive to collect.

Fig 13.2.3: Overall flow diagram of the manufacture of Sulphuric acid

• Chemical properties of Sulphur
• Sulphur exhibits oxidation numbers of -2, 0, +2, +4 and +6.
• Oxidation number -2 is seen in the sulphide ion, S2-, and a typical compound
is H2S, hydrogen sulphide or hydrosulphuric acid.
• Sodium sulphide, Na2S, is an ionic compound of sodium with -2sulphur.
• The compounds Na2S4 and Na2S5, and many other similar sulphides, are
easily recognized as short bits of sulphur chains that have picked up a
sodium ion at each end, or more probably just two electrons.
• Hydrogen sulphide burns in air to form sulphur dioxide.
• Hydrogen sulphide is said to be a reducing agent in these reactions. On the
other hand, +6 sulphur, as in sulphuric acid, is a strong oxidizing agent.
• There are many different stable sulphur oxides, but the two that are
commonly found are sulphur dioxide and sulphur trioxide.
Industrial importance of Sulphuric acid
• The largest use of sulphuric acid in industry is in the fertiliser industry.
• The sulphuric acid is mostly used in production of phosphoric acid, which in turn used to
manufacture fertilizers such as triple superphosphate, mono and di-ammonium
phosphates.
• Sulphuric acid is also used for producing superphosphate and ammonium sulphate.
• Production of ammonium sulphate in industry is produced from gypsum(CaSO4·2H2O)as
shown below,
(𝑁𝐻4 )2 𝐶𝑂3 + 𝐶𝑎S𝑂4 → (𝑁𝐻4 )2 𝑆𝑂4 + 𝐶𝑎𝐶𝑂3
• Finely divided gypsum is added to an ammonium carbonate solution. Calcium carbonate
precipitates as a solid, leaving ammonium sulphate in the solution.
• Ammonium sulphate occurs naturally as the rare mineral mascagnitein
volcanic fumaroles and due to coal fires on some dumps.
• Sulphuric acid can be used as an acidic dehydrating reaction medium in organic
chemical and petrochemical processes involving such reactions as nitration,
condensation, and dehydration, as well as in oil refining, in which it is used for refining,
alkylation, and purification of crude-oil distillates.
• In the inorganic chemical industry Sulphuric acid is used in the production of Titanium
oxide (TiO2) pigments, hydrochloric acid, and hydrofluoric acid.
• In the metal processing industry, sulphuric acid is used for pickling and
descaling steel, for leaching copper, uranium and vanadium ores in
hydrometallurgical ore processing, and in the preparation of electrolytic
baths for nonferrous-metal purification and plating.
• Certain wood pulping processes in the paper industry require sulphuric acid,
used in textile and chemical fibre processes and leather tanning.
• Sulphuric acid is used in the manufacture of explosives, detergents and
plastics.
• Sulphuric acid is used in production of dyes and pharmaceuticals.
Compounds of Sulphur
• Sulphur oxides (SOx) are compounds of sulphur and oxygen molecules.
• Sulphur dioxide, at room temperature is a toxic, non-flammable, colourless
gas that is heavier than air. It has a strong pungent and irritating odour
• Sulphur dioxide (SO2) is the predominant form found in the lower
atmosphere.
Major Sources of Sulphur dioxide
• Most sulphur dioxide is produced by burning fuels containing sulphur or by roasting metal
sulphide ores, although there are natural sources of sulphur dioxide (accounting for 35–65% of
total sulphur dioxide emissions) such as volcanoes.
• Thermal power plants burning high-sulphur coal or heating oil are generally the main sources of
anthropogenic Sulphur dioxide emissions worldwide, followed by industrial boilers and
nonferrous metal smelters.
• Emissions from domestic coal burning and from vehicles can also contribute to high local
ambient concentrations of Sulphur dioxide.
Effects on the environment
• Sulphur dioxide (SO2) is chemically unstable, therefore when it enters the atmosphere it will react
with oxygen (O2) to produce Sulphur trioxide (SO3).
• Sulphur trioxide, which is extremely hygroscopic (absorbs moisture), will react with atmospheric
water (H2O) to produce a mist of Sulphuric acid (H2SO4).
• The Sulphuric acid may either fall to the ground as precipitation (acidic rain) or it may further
react with metal oxides, as part of dust particles, to form Sulphates (SO42- ) such as ammonium
Sulphates which are also acidic.
• Trees and other plants exposed to wet and dry acid depositions will be damaged this has an
impact on forest ecosystems.
• Agricultural crops may also be damaged by exposure to acid rain depositions. Cereal crops are
affected more.
• Exposure of agricultural crops to acid rain affects the yields of most crops.
Sulphur dioxide in food preservation
• Sulphur dioxide is widely used in the food and drinks industries for its
properties as a preservative and antioxidant.
• Sulphur dioxide is used as a preservative because it works as an
antimicrobial preventing the growth of bacteria, mould, and fungus; an
antioxidant preventing rancidity; and as a chemical that attacks enzymes
that cause discoloration, ripening, and rotting, usually in fruits after harvest.
Through the process of plasmolysis plant and food cells are altered by
contraction and separation through the loss of water.
• Sulphite preservation causes these cells to die instead of being transferred
quickly to a water solution.
• Mazowe orange crush is preserved with SO2.
Preparing ammonium sulphate in the laboratory
• Ammonium Sulphate can be made in the laboratory by neutralising dilute Sulphuric acid
with ammonia solution.
2𝑁𝐻3 + 𝐻2 S𝑂4 → (𝑁𝐻4 )2 𝑆𝑂4
Aim: To prepare ammonium sulphate solution
Apparatus and materials
• Evaporating basin and a full range indicator paper
• Bunsen burner, tripod and gauze
• 50 cm3 measuring cylinder
• Filter funnel and filter paper
• Conical flask to collect filtrate
• Watch glass and rod
• 1 mol dm−3sulphuric acid, 25 cm3
• 2 mol dm−3 ammonia solution, 25 cm3
Procedure
• Care: Wear eye protection.
1. Using a measuring cylinder, measure out 20 cm3 of 1 mol dm-3sulphuric acid into an
evaporating basin.
2. Wash the measuring cylinder and then add about 25 cm3 of 2 mol dm−3 ammonia solution to it.
Slowly add the ammonia solution to the evaporating basin, stirring the solution as you do so. After
you have added about 15 cm3 check with indicator paper to see if the pH has reached 7. Add
further 1 cm3 amounts of ammonia solution if necessary, checking the pH after each addition, until
the pH is 7 or above.
3. Put the evaporating basin on a tripod and gauze. Slowly evaporate the solution until it is about one-
fifth of its original volume. Caution: Do not boil the solution as it may spit.
4. Allow the concentrated solution to cool until crystals form.
5. Filter off the crystals and put the filter paper and crystals on a watch glass and dab dry with another
piece of filter paper. Cover them with a piece of clean filter paper and leave them to dry at room
temperature.
6. Label a sample tube with the name of the product, your name and the date. Weigh the labelled
sample tube and record its mass.
7. Tip your dry product into the sample tube. Weigh the tube again. Record its mass.

Expected observation
• Blue Litmus paper will turn purple in the solution containing the acid as more ammonia is being
added.
Conclusion
• Since reaction of Ammonia and Sulphuric acid is an acid base reaction a salt and water is formed by
evaporating leaves the salt behind.
 ASSESSMENT EXERCISE 13.2 SULPHUR COMPOUNDS

1. During the production of sulphuric acid the reaction in the converter is given by the
equation:
2𝑆𝑂2 (𝑔)+𝑂2 𝑔 ⇋ 2𝑆𝑂3 (𝑔)∆H= -197 KJ/mol
Explain the effect of the following changes on the rate of reaction and yield at equilibrium.
a. Increased applied pressure at constant temperature. [3]
b. Increased temperature at constant volume. [3]
c. The addition of excess O2 at constant temperature and volume. [2]
d. Sulphur dioxide gas is passed over a catalyst. What is the catalyst and what is its purpose? [3]
e. Name two industrial products which are made using sulphuric acid? [2]