GCSE OCR Gateway Chemistry
C6.1d-e The Contact process to make Sulfuric acid.
C6.1d To be able
to explain the trade-off between rate of production of a desired product and
position of equilibrium in some industrially important processes e.g. the
Contact process
C6.1e To be able to interpret
graphs of reaction conditions versus rate
The Contact process for the manufacture of Sulphuric
acid H2SO4
It used to
be said I think originally by Justus von Liebig of condenser fame, that a
country’s economic success and prosperity was best judged from its levels of
sulphuric acid production.
Sulphuric
acid is still a key basic chemical made in vast quantities the world over
today. And still produced by a not very green process involving the use of high
temperature, burning sulphur and vanadium catalysts.
By the way
it is called the Contact process because of the way gases come into contact
(!!) with the catalyst.
The Internet
will give you a host of different flow diagrams to reveal the different stages
in the manufacture. Here is one:
Basically,
there are three stages
1.
Sulphur is
burned in oxygen
2.
Sulphur
dioxide is oxidised to sulphur trioxide
3.
Sulphur
trioxide is added to water to make the acid.
Of course,
if it were that simple we wouldn’t have the process on an examination
course. In other words, there has to be
a catch somewhere.
So let’s
look more closely at the basic process.
Stage One: The oxidation of sulphur
Raw
materials for the manufacture of sulphuric acid are air (oxygen O2)
water (H2O) and sulphur (S8).
In stage one
sulphur is burned in excess oxygen excess because the excess will be sued in
the next stage to oxidised the sulphur dioxide to sulphur trioxide.
Equation: S8 (l) +
8O2 (g) ⟶
8SO2 (g)
The sulphur
is used in its liquid form and sprayed in to the burner with air where it
burned easily with a distinctive blue flame as you can see in the photos below:
The first photo
shows sulphur burning in the industrial process the second shows the element
burning in a gas jar of oxygen in the lab.
Pumping the
gases through process at a pressure just above atmospheric pressure is enough
to maintain the equilibrium producing sulphur trioxide in the second stage.
Stage two: Oxidation of sulphur dioxide to
sulphur trioxide
This stage
requires a vanadium(V)oxide (V2O5) catalyst. It is featured in the photo below from BASF.
Equation: 2SO2 (g) + O2
(g) ⇌ 2SO3
(g)
This reaction
is exothermic in the forward direction so that any increase in temperature will
reduce the yield of sulphur trioxide.
But the temperature has to be a compromise because the catalyst will
only operate effectively above about 400oC.
The graph
shows the way temperature affects yield of sulphur trioxide.
But if the
gas mixture of sulfur dioxide and oxygen is pumped over catalyst beds in
succession and in between cooled down then the equilibrium does not have time
to readjust before entering a second catalyst bed and converting even more
sulphur dioxide to trioxide.
This
approach eventually converts about 97% of the sulphur dioxide to the trioxide
leaving about 3% of gases to recycle.
The diagram
here shows how the multistage catalyst bed in use.
A low
pressure of about 2 atmospheres is enough to push the gases through the
catalyst beds and as three moles of molecules turn into two moles a slight
increase in pressure pushes the equilibrium to favour the products.
The
resultant gas mixture of sulphur trioxide is now turned into sulphuric acid.
Stage Three: Production of sulphuric acid (H2SO4)
When very
hot sulphur trioxide meets water vapour a pungent, corrosive mist of
concentrated sulphuric acid forms. This
is dangerous since it is corrosive and toxic and it is very difficult to
condense into liquid form.
To get over
this problem the sulphur trioxide is bubbled into concentrated sulphuric acid rather
than water, to form a very corrosive and fuming liquid called oleum.
Equation: H2SO4 (l) +
SO3(g) ⟶
H2S2O7 (l)
The oleum
formed can the be diluted with water to form twice the molar quantity of
concentrated sulphuric acid
Equation: H2S2O7 (l) +
H2O (l) ⟶
2H2SO4 (l)
The liquid
concentrated sulphuric acid is about 99% acid and is transported to other
users.
It is often
said that the cooling of the gas mixtures in stage two generates enough steam
to heat the industrial plant offices and generate enough electricity to power
the plant’s pumps and other needs.