[Link]
htm
3. Why is sulphuric acid a useful material? How is it made? Contact Process
Because sulfuric acid has so many uses the industrial development of a country is sometimes measured
by the amount of sulphuric acid that is used each year. Sulphuric acid is made starting from the element
sulphur which is found in the Earth's crust.
Sulphuric acid is used as the lead-acid battery, the manufacture of detergents, dyes
Dyestuffs), explosives, artificial fibres, pigments like white titanium dioxide and is used to
make fertilisers,
o e.g. ammonia + sulphuric acid ==> ammonium sulphate (a fertiliser salt)
o 2NH3(aq) + H2SO4(aq) ==> (NH4)2SO4(aq) => evaporation to get crystals
o Lots more equations on the Acids, Bases, pH and Salts pages.
o Its acid action make it good for cleaning metal surfaces in industry e.g. by dipping the
object into a bath of sulfuric acid.
o Concentrated sulphuric acid is used in making dyestuffs and explosives.
Sulphuric acid is manufactured from the raw materials sulphur, air and water and involves the
production of sulphur trioxide in the Contact Process.
(1) Sulfur is burned in air to form sulphur dioxide (exothermic).
o In the reaction the sulphur is oxidised (O gain) (1a) S(s) + O2(g) ==> SO2(g)
o Sulfur dioxide can also be indirectly obtained from the process of extracting copper from
copper sulphide ores e.g. in a copper smelter: (1b) Cu2S(s) + O2(g)==> 2Cu(l) + SO2(g)
Note: Sulphur dioxide itself is a useful chemical in its own right:
o It is used as a bleach in the manufacture of wood pulp for paper manufacture
o and its toxic nature makes it useful as a food preservative by killing bacteria.
(2) In the reactor, the sulphur dioxide is mixed with air (to give the required SO2:O2 2:1 ratio) and
the mixture passed over a catalyst of vanadium(V) oxide V205(vanadium pentoxide) at a high
temperature (about 450°C) and at a pressure of between one and two atmospheres. It is a 2nd
exothermic oxidation and is known as the Contact Process.
In the reactor the sulphur dioxide is oxidised in the reversible exothermic reaction ...
o (2) 2SO2(g) + O2(g) 2SO3(g)
The reaction forms sulphur trioxide and the equilibrium is very much to the right hand side ...
o So, despite the reaction being exothermic (95 kJ released per mole of SO3), a relatively
high temperature is used to ensure a reasonable rate of reaction (despite the fact
that it favours reverse reaction R to L, from the energy change equilibrium rule, inc. T.
favours endothermic direction).
o The reaction is favoured by high pressure (pressure equilibrium rule, 3 => 2 gas
molecules, LHS ==> RHS), but only a small increase in pressure is used to give high
yields of sulphur trioxide, because the formation of SO3 on the right hand side is so
energetically favourable (approx. 99% yield, i.e. only about 1% SO2 unreacted).
o The use of the V2O5 catalyst ensures a fast reaction without having to use too a higher
temperature which would favour the left hand side and reduce the yield BUT it does not
change the % of sulphur trioxide formed, you simply get there faster.
o More GCSE notes on reversible reactions and equilibrium rules. Advanced Level
notes on ...
(3) The sulphur trioxide is dissolved in concentrated sulphuric acid to form fuming sulphuric acid
(oleum).
o SO3(g) + H2SO4(l) ==> H2S2O7(l)
(4) Water is then carefully added to the oleum to produce concentrated sulphuric acid (98%).
o H2S2O7(l) + H2O(l) ==> 2H2SO4(l)
o If the sulphur trioxide is added directly to water an acid mist forms which is difficult to
contain because the reaction to form sulphuric acid solution is very exothermic!
o If you 'add' equations (3) + (4) you get
(5) SO3(g) + H2O(l) ==> H2SO4(l)
which is how it is usually written in GCSE textbooks, so learn
equations (1a), (2) and (5) for the manufacture of sulfuric acid from sulfur.
Good anti-pollution measures need to be in place since the sulphur oxides are harmful and
would cause local acid rain! To help this situation AND help the economics of the process, any
unreacted sulphur dioxide is recycled through the reactor.
Concentrated sulphuric acid can be used in the laboratory as a dehydrating agent.
o Dehydration is the removal of water or the elements of water from a compound and
can be described as an elimination reaction. Usually and adjacent H and OH in a
molecule are removed to form the water.
o When added to some organic compounds containing hydrogen and oxygen, e.g. sugar,
concentrated sulphuric acid removes the elements of water from the compound leaving a
'spongy' black carbon residue.
o If alcohols are heated with conc. sulphuric acid, they are dehydrated to alkenes.
e.g. ethanol ==> ethene + water
CH3CH2OH ==> CH2=CH2 + H2O
o When added to blue copper sulphate crystals concentrated sulphuric acid removes the
water of crystallisation leaving white anhydrous copper sulphate. In this case the water
already exists BUT not in a mixture and so the following reaction is classified as a
chemical change.
CuSO4.5H2O(s) CuSO4(s) + 5H2O(absorbed into the H2SO4 which it reacts with)
o Conc. H2SO4 catalyses the reaction between an alcohol and carboxylic acid to form
an pleasant smelling ester liquid but it isn't considered a dehydration reaction (H comes
from one molecule and OH from the other).
e.g. the esterification ethanoic acid + ethanol ==> ethyl ethanoate + water
CH3COOH + CH3CH2OH ==> CH3COOCH2CH3 + H2O
o Concentrated sulphuric acid can be used as a drying
agent e.g. in the preparation of gases.
The prepared gas is bubbled through
a dreschel/dreschler bottle (illustrated on the right),
containing the concentrated sulphuric acid. In this
case the water vapour is just a component in a
gaseous mixture. Most gases can be dried in this
way except the alkaline gas ammonia which will
exothermically react to form a solid salt. In this case the water vapour is just a
component in a gaseous mixture.
*
Properties of Sulfuric Acid (H2SO4)
Sulfuric acid is a diprotic acid (can donate 2 protons to a base)
Sulfuric acid ionises in water in two stages:
H2SO4(l) + H2O(l) -----> HSO4-(aq) + H3O+(aq)
HSO4-(aq) + H2O(l) SO42-(aq) + H3O+(aq)
Sulfuric acid is a strong acid (complete dissociation in water, Ka approaches infinity)
Sulfuric acid reactions:
sulfuric acid + metal -----> metal sulfate + hydrogen gas
sulfuric acid + carbonate -----> metal sulfate + carbon dioxide gas + water
sulfuric acid + base -----> salt + water
sulfuric acid + ammonia -----> ammonium sulfate
Sulfuric acid can take part in redox reactions.
Uses of Sulfuric Acid (H2SO4)
Sulfuric acid is the electrolyte used in lead-acid batteries (accumulators)
Sulfuric acid is important in the production of fertilizers such as ammonium sulfate (sulfate of ammonia),
(NH4)2SO4, and superphosphate, Ca(H2PO4)2, which is formed when rock phosphate is treated with sulfuric
acid.
Sulfuric acid is used to remove oxides from iron and steel before galvanising or electroplating
Concentrated sulfuric acid (18M) is used as a dehydrating agent, that is, to remove water, since it has a
tendency to form hydrates such as H2SO4.H2O, H2SO4.2H2O, etc.
Sulfuric acid is often used to dry neutral and acidic gases such as N2, O2, CO2 and SO2
Sulfuric acid will "suck" water out of carbohydrates and some other organic compounds which contain
oxygen and hydrogen. For example, sulfuric acid will "suck" water out of sucrose, C12H22O11(s), (cane
sugar) to produce a spongy mass of carbon:
C12H22O11(s) + 11H2SO4 -----> 12C(s) + 11H2SO4.H2O
Sulfuric acid is used in the production of nitroglycerine, an inorganic ester & organic nitrate, which is used
as an explosive but can also be used as a vasodilator, a substance that dilates blood vessels and can
be used in the treatment of certain types of heart disease:
CH2ONO2
|
CHONO2
|
CH2ONO2
Manufacture of Sulfuric Acid (H2SO4)
Most of the sulfuric acid manufactured is produced using the Contact Process.
Absorption Tower
Combustion Hydration of
Converter (sulfur trioxide
Chamber -- -- -- Oleum
(conversion of sulfur absorbed
(combustion of > > > to produce sulfuric
dioxide) into the sulfuric acid
sulfur) acid
mist
The Contact Process is a process involving the catalytic oxidation of sulfur dioxide, SO2, to sulfur trioxide, SO3.
I. Solid sulfur, S(s), is burned in air to form sulfur dioxide gas, SO2
S(s) + O2(g) -----> SO2(g)
II. The gases are mixed with more air then cleaned by electrostatic precipitation to remove any particulate
matter
III. The mixture of sulfur dioxide and air is heated to 450oC and subjected to a pressure of 101.3 - 202.6 kPa (1
-2 atmospheres) in the presence of a vanadium catalyst (vanadium (V) oxide) to produce sulfur trioxide, SO 3(g),
with a yield of 98%.
2SO2(g) + O2(g) -----> 2SO3(g)
IV. Any unreacted gases from the above reaction are recylced back into the above reaction
V. Sulfur trioxide, SO3(g) is dissolved in 98% (18M) sulfuric acid, H2SO4, to produce disulfuric acid or
pyrosulfuric acid, also known as fuming sulfuric acid or oleum, H2S2O7.
SO3(g) + H2SO4 ------> H2S2O7
This is done because when water is added directly to sulfur trioxide to produce sulfuric acid
SO3(g) + H2O(l) -----> H2SO4(l)
the reaction is slow and tends to form a mist in which the particles refuse to coalesce.
VI. Water is added to the disulfuric acid, H2S2O7, to produce sulfuric acid, H2SO4
H2S2O7(l) + H2O(l) -----> 2H2SO4(l)
The oxidation of sulfur dioxide to sulfur trioxide in step III above is an exothermic reaction(energy is released),
so by Le Chatelier's Principle, higher temperatures will force the equilibrium position to shift to the left hand
side of the equation favouring the production of sulfur dioxide.
Lower temperatures would favour the production of the product sulfur trioxide and result in a higher yield.
However, the rate of reaching equilibrium at the lower temperatures is extremely low.
A higher temperature means equilibrium is established more rapidly but the yield of sulfur trioxide is lower.
A temperature of 450oC is a compromise whereby a faster reaction rate results in a slightly lower yield.
Similarly, at higher pressures, the equilibrium position shifts to the side of the equation in which there are the least
numbers of gaseous molecules.
2SO2(g) + O2(g) -----> 2SO3
On the left hand side of the reaction there are 3 moles of gaseous reactants, and the right hand side there are 2 moles
of gaseous products, so higher pressure favours the right hand side, by Le Chatelier's Principle.
Higher pressure results in a higher yield of sulfur trioxide.
A vanadium catalyst (vanadium (V) oxide) is also used in this reaction in order to speed up the rate of the reaction.
[Link]