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Unit 4 Rates, equilibria and further organic chemistry

Chapter 3 Equilibrium
4.5 Equilibria
dynamic equilibrium
A reversible reaction is a chemical change in which the products can be converted back to the original
reactants under suitable conditions.
o In a reversible reaction, changing the reaction conditions e.g. concentration, pressure or temperature
will change the net direction the reaction goes i.e. more to the right (forward) or more to left
(backward).
This means the reaction can go in either direction i.e.
o A + B ==> C + D or C + D ==> A + B
Industrial processes
For industrial processes, it is important to maximise the concentration of the desired products and minimise
the 'leftover' reactants. Le Chatelier's Principle and the principles of reaction kinetics can both be used to
design the best reaction conditions to give the highest possible yield of product in an economic way.

Methanol production
Methanol is an important alcohol used in fuel mixtures, making methyl esters and oxidation to methanol
(formaldehyde) to make urea-formaldehyde resin glues.
It is manufactured directly from synthesis gas (CO + H
2
).
CO
(g)
+ 2H
2(g)
CH
3
OH
(g)
(H = -90 kJ mol
-1
)

K
p
=
p
CH3OH

---------------
p
CO
p
H2
2

The reaction is carried out at 250
o
C, over a Cu-ZnO-Al
2
O
3(alumina)
catalyst at a pressure of 5-10 x 10
6
Pa (5-
10MPa, 50-100 atm).
Theoretically the reaction is favoured by high pressure (3 gas mol ==> 1 gas mol) and low temperature.
In practice a high pressure is used to give an acceptable yield in accordance with Le Chatelier's Principle, but
a moderately high temperature plus a catalyst, are employed to get an economic production rate.
The Contact Process in the manufacture of sulphuric acid
The mechanism of the Contact Process is discussed on the AS-A2 Transition Metals page but its the
application of equilibrium and kinetic concepts which is important here.
The Contact Process of sulphur trioxide production must be economically efficient for the
manufacture of the important industrial chemical sulphuric acid.
In the Contact Process reactor the sulphur dioxide is mixed with air (the required stoichiometric volume/mole
SO
2
:O
2
ratio is 2:1, in practice 1-2:1 is used) and the mixture passed over a catalyst of vanadium(V) oxide
V
2
0
5
at a relatively high temperature of about 450C and at a pressure of between 1-2 atm. It is an exothermic
oxidation and is known as the .
(1) In the reactor the sulphur dioxide is oxidised in the reversible exothermic reaction ...
o 2SO
2(g)
+ O
2(g)
2SO
3(g)
(H = -196 kJ mol
-1
)
o
K
p
=
p
SO3
2

----------------
p
SO2
2
p
O2

The reaction forms sulphur trioxide and the equilibrium is very much to the right hand side because
o Despite the reaction being exothermic a relatively high temperature is used which favours the
reverse reaction R to L, from the energy change equilibrium rule, i.e. increasing temperature shifts the
equilibrium in the endothermic direction. However the value of K
p
is high enough to give a 99% yield.
o The reaction is favoured by high pressure (pressure equilibrium rule, 3 => 2 gas molecules), but
only a small increase in pressure is used to give high yields of sulphur trioxide, because the right
hand side is energetically very favourable (quite exothermic and high K
p
)
o The use of the V
2
O
5
catalyst ensures a fast reaction without having to use too a higher
temperature which would begin to favour the left hand side too much (energy change equilibrium
rule), but remember a catalyst does not affect the % yield or equilibrium concentration of SO
3
, you just
get there more economically faster.
o Multiple reactor beds are used to ensure the maximum % conversion and heat exchange
systems are used to control the temperature, and pre-heat incoming reactant gases.
o 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 the residual
SO
2
is kept to the minimum by the reaction conditions describe above.
(2) The sulphur trioxide is dissolved in concentrated sulphuric acid to form fuming sulphuric acid (oleum).
o SO
3(g)
+ H
2
SO
4(l)
==> H
2
S
2
O
7(l)

(3) Water is then carefully added to the oleum to produce concentrated sulphuric acid (98% H
2
SO
4
).
o H
2
S
2
O
7(l)
+ H
2
O
(l)
==> 2H
2
SO
4(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 with a big K value!
Lime production from limestone
calcium carbonate (limestone) calcium oxide (lime) + carbon dioxide
CaCO
3(s)
CaO
(s)
+ CO
2(g)
(H = +178 kJ mol
-1
)
The concentration of the solids is constant, so the only effective equilibrium expression is:
o K
p
= p
CO2
atm or Pa
The forward reaction is endothermic, 178kJ of heat energy is absorbed (taken in) for every mole of calcium
oxide formed and so CaO formation is favoured by high temperature. In fact the reaction is not viable/feasible
until at least 900
o
C, and at 1000
o
C in a limekiln the equilibrium position is very much on the RHS.
One mole of gas is formed in the process, so there is a net increase in the moles of gas in lime formation,
since there are no gaseous reactants. Therefore decreasing the pressure will favour the formation of more
gas molecules if possible, so more carbon dioxide formed, and hence more lime.
However, the reaction is carried out at normal atmospheric pressure in a lime kiln that that is well ventilated.
This reduces the partial pressure of carbon dioxide and so reduces the un-desired backward reaction. It
means that a true equilibrium is never established because the reaction is not in a closed system and so as
CO
2
is vented, the forward reaction is promoted.
Old kilns essentially worked on a batch process i.e. coal fuelled furnace heating adjacent limestone, but
modern tilted rotary kilns run continually with limestone fed in at one end and lime extracted at the other end.

4.6 Application of rates and equilibrium

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