SULPHUR AND ITS COMPOUNDS

Sulphur

Sulphur occurs as the free element chiefly in Texas and Louisiana, U.S.A. It is
extracted by pumping super-heated water into the underground sulphur beds, which
forces molten sulphur to the surface.
Sulphur occurs as the element in many volcanic areas, it also occurs naturally a
s metal sulphides (eg. iron pyrites) and sulphates (eg. gypsum, hydrated calcium
sulphate). Crude oil and natural gas contain sulphur as an impurity. Since the
sulphur must be removed anyway to reduce pollution, these are important sources
of sulphur.
Sulphur is a yellow solid which can be easily melted. When heated in air or oxyg
en, it burns with a blue flame giving sulphur dioxide.
S + O2 ® SO2
Most sulphur is used to make sulphur dioxide which is then used mainly to make s
ulphuric acid. Some sulphur is used in the vulcanisation (hardening) of rubber f
or car tyres, as a fungicide, and in making gunpowder and matches.
Uses of Sulphur Dioxide
Sulphur dioxide is used mainly in the manufacture of sulphuric acid (see next pa
ge). Sulphur dioxide is also used to bleach the yellow dye in paper, straw and w
ool. It does this by reducing the natural yellow dye to a colourless compound. I
t is used in paper-making (sulphites are used to separate the cellulose from the
rest of the wood), as a fumigant (gas for killing pests), and as a preservative
for some foodstuffs.
Sulphur Dioxide as a Pollutant
Sulphur dioxide occurs in the waste gases from the burning of oil, coal and othe
r substances containing sulphur. It is therefore often found as an air pollutant
; especially around factories and cities. Sulphur dioxide forms tiny drops of su
lphurous acid in moist air and some of this is oxidised to sulphuric acid. These
compounds irritate the respiratory system, cause "acid rain", increase the weat
hering of buildings and the rusting of iron and steel, and kill fish in lakes.

SULPHURIC ACID
Sulphuric acid is manufactured by the Contact Process in the following steps:-
1. Sulphur dioxide is produced. This can be done in a number of ways eg. by burn
ing sulphur in
air.
S + O2 ® SO2
also i) by burning hydrogen sulphide from crude oil and natural gas.
ii) by roasting sulphide ores such as zinc blende, ZnS, in air.
2. The sulphur dioxide is dried and purified (to protect the catalyst).
3. The sulphur dioxide is oxidised to sulphur trioxide in the following way:-
Sulphur dioxide mixed with excess air is passed over a vanadium (V) oxide cataly
st at about
450oC. The reaction is exothermic and no external heat is needed once it has sta
rted (this is
important economically because it greatly reduces fuel costs).

4. The sulphur trioxide is then converted to sulphuric acid.

H2O + SO3 ® H2SO4
This is NOT done directly by adding the sulphur trioxide to water, because the r
eaction is
violent and forms a great deal of acid mist. Instead the sulphur trioxide is dis
solved in 98%
sulphuric acid forming the 100% acid (or with further absorbtion, a liquid calle
d "oleum",
H2S2O7). The 100% acid or the oleum may then be carefully diluted with water to
give the
ordinary 98% concentrated acid.

Reactions of Sulphuric acid

Sulphuric acid is a strong acid, i.e. it is completly ionised in dilute solution
(weak acids are only slightly ionised)
H2SO4 2H+ + SO42-
Dilute sulphuric acid has the following typical acid reactions:-
a) It turns litmus red.
b) It reacts with many metals forming a sulphate and hydrogen.
eg. Mg + H2SO4 ® MgSO4 + H2
c) It reacts with bases forming a salt and water.
eg. 2NaOH + H2SO4 ® Na2SO4 + 2H2O
(When half-neutralised it forms the acid salt, sodium hydrogen sulphate, NaHSO4)
d) It reacts with carbonates forming a sulphate, water and carbon dioxide.
eg. CuCO3 + H2SO4 ® CuSO4 + H2O + CO2
Uses of Sulphuric Acid
Sulphuric acid is mainly used in the manufacture of "superphosphate" fertilizer.
The second biggest use is in the manufacture of ammonium sulphate fertilizer. T
he acid has many other uses such as making pigments (for paints), rayon, deterge
nts and metal sulphates. It is the electrolyte in car batteries.
Economics of Sulphuric Acid Manufacture
Sulphuric acid is manufactured on a very large scale, and it is a relatively che
ap chemical. To be competitive it must be produced as cheaply as possible. Manuf
acturing plants are therefore sited so that the raw materials:- air, water and s
ulphur dioxide are obtained very cheaply or free. To lower transport costs, the
plants are sited close to major users of the acid (eg. fertilizer plants). To lo
wer fuel costs, heat given out during the reaction is used to keep the catalyst
at the right temperature.

Test for a Sulphate

To a solution of the substance add barium chloride solution. If there is a white
precipitate, add dilute hydrochloric acid. If the white ppt. does not dissolve,
the original substance is a sulphate.

Preparation of Sulphates
Most sulphates are prepared by the usual methods for preparing salts i.e. action
of sulphuric acid on an insoluble base, metal or carbonate, filtering off the e
xcess insoluble substance, then evaporating the filtrate to obtain crystals.
Sodium and potassium sulphates are prepared by titration. Lead and barium sulpha
tes are insoluble. They are prepared by precipitation.