5 Equilibria

5.
Equilibria
Many reactions are reversible All reversible reactions reach an
N2 + 3H2 2NH3 dynamic equilibrium state.
We use the expression ‘position of

Dynamic equilibrium occurs when forward and
equilibrium’ to describe the composition of the
backward reactions are occurring at equal rates. The
equilibrium mixture.
concentrations of reactants and products stays
constant and the reaction is continuous.
If the position of equilibrium favours the
reactants (also described as “towards the left”)
then the equilibrium mixture will contain mostly
reactants.
Le Chatelier’s Principle
We use Le Chatelier’s principle to work out how Le Chatelier’s principle states that if an external
changing external conditions such as temperature condition is changed the equilibrium will shift to
and pressure affect the position of equilibrium oppose the change (and try to reverse it).
Effect of Temperature on equilibrium

Typical Exam question: What effect would increasing
If temperature is increased the equilibrium will
temperature have on the yield of ammonia?
shift to oppose this and move in the
endothermic direction to try and reduce the N2 + 3H2 2NH3 ∆H = -ve exo
temperature by absorbing heat.
Exam level answer : must include bold points
And its reverse
If temperature is increased the equilibrium will
shift to oppose this and move in the endothermic,
If temperature is decreased the equilibrium
backwards direction to try to decrease
will shift to oppose this and move in the
temperature. The position of equilibrium will shift
exothermic direction to try and increase the
towards the left, giving a lower yield of ammonia.
temperature by giving out heat.
Low temperatures may give a higher yield of product but will also result in slow rates of
reaction. Often a compromise temperature is used that gives a reasonable yield and rate
Effect of Pressure on equilibrium

Typical Exam question: What effect would increasing
Increasing pressure will cause the equilibrium to shift
pressure have on the yield of methanol?
towards the side with fewer moles of gas to oppose
the change and thereby reduce the pressure. CO (g) + 2H2(g) CH3OH (g)
And its reverse

Exam level answer : must include bold points
If pressure is increased the equilibrium will shift
Decreasing pressure will cause the equilibrium to shift to oppose this and move towards the side with
towards the side with more moles of gas to oppose fewer moles of gas to try to reduce the
the change and thereby increase the pressure. pressure . The position of equilibrium will shift
towards the right because there are 3 moles of
If the number of moles of gas is the same on both gas on the left but only 1 mole of gas on the right,
sides of the equation then changing pressure will have giving a higher yield of methanol.
no effect on the position of equilibrium
H2 + Cl2 2HCl
Increasing pressure may give a higher yield of product and will produce a faster rate. Industrially high
pressures are expensive to produce ( high electrical energy costs for pumping the gases to make
a high pressure) and the equipment is expensive (to contain the high pressures)
N Goalby chemrevise.org 1
Effect of Concentration on equilibrium
Increasing the concentration OH- ions causes the equilibrium to shift to
I2 + 2OH- I- + IO- + H2O oppose this and move in the forward direction to remove OH- ions. The
position of equilibrium will shift towards the right, giving a higher yield
brown colourless
of I- and IO-. ( The colour would change from brown to colourless)
Adding H+ ions reacts with the OH- ions and reduces their concentration
so the equilibrium shifts back to the left giving brown colour.
Effect of Catalysts on equilibrium

A catalyst has no effect on the position of equilibrium, but it will speed up the rate at which the
equilibrium is achieved.
It does not effect the position of equilibrium because it speeds up the rates of the forward and
backward reactions by the same amount.
Importance of equilibrium to industrial processes
You should be able to apply the above ideas to given reactions

Common examples
Contact process
Haber process
Stage 1 S (s) + O2 (g) SO2 (g)
N2 + 3H2 2NH3 ∆H = -ve exo
Stage 2 SO2 (g) + ½ O2 (g) SO3 (g) ∆H = -98 kJ mol-1
T= 450oC, P= 200 – 1000 atm, catalyst = iron
T= 450oC, P= 10 atm, catalyst = V2O5
Low temp gives good yield but slow rate:
Low temp gives good yield but slow rate: compromise
compromise temp used
moderate temp used
High pressure gives good yield and high rate:
High pressure gives slightly better yield and high rate: too
too high a pressure would lead to too high
high a pressure would lead to too high energy costs for
energy costs for pumps to produce the pressure
pumps to produce the pressure
Hydration of ethene to produce ethanol

Production of methanol from CO
CH2=CH2 (g) + H2O (g) CH3CH2OH(l) ∆H = -ve
CO (g) + 2H2(g) CH3OH (g) ∆H = -ve exo
T= 300oC, P= 70 atm, catalyst = conc H3PO4
T= 400oC, P= 50 atm, catalyst = chromium and
zinc oxides Low temp gives good yield but slow rate: compromise
temp used
Low temp gives good yield but slow rate:
compromise temp used High pressure gives good yield and high rate: too high a
pressure would lead to too high energy costs for pumps
High pressure gives good yield and high rate:
to produce the pressure
too high a pressure would lead to too high
energy costs for pumps to produce the pressure High pressure also leads to unwanted polymerisation of
ethene to poly(ethene)
In all cases catalysts speeds up the rate allowing lower temp to be used (and hence lower energy costs)
but have no effect on equilibrium
In all cases high pressure leads to too high energy costs for pumps to produce the pressure and
too high equipment costs to have equipment that can withstand high pressures.
Recycling unreacted reactants back into the reactor can improve the overall yields of all these processes
2
N Goalby chemrevise.org

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5 Equilibria

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5.

We use the expression ‘position of

Effect of Temperature on equilibrium

Effect of Pressure on equilibrium

And its reverse

Effect of Catalysts on equilibrium

Importance of equilibrium to industrial processes

You should be able to apply the above ideas to given reactions

Hydration of ethene to produce ethanol

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