Equilibria

Introduction
Many reactions do not go to
complete because the reaction is
reversible. As the reaction is
dependent on the concentration of
the reactants, the reaction will
proceed up to the point at which the
rate of the forward reaction equals the
rate of the reverse reaction.


Equilibria

Things to learn
• At equilibrium, the rate of forward
reaction equals the rate of the reverse
reaction.
• Both products and reactants are
constantly being made and used up, but
their concentrations do not change.
• In a static equilibrium all the processes
which might disturb the equilibrium have
stopped.

Equilibria
• Static equilibrium can be demonstrated by
two children on a see-saw. They are
balancing each other so no movement of
the see-saw takes place.
• Dynamic equilibrium can be demonstrated
by using isotopes. For example:
CH
3
COOH(l) + C
2
H
5
OH(l) CH
3
COOC
2
H
5
(l) + H
2
O(l)
• Mix the four substances in their equilibrium
concentrations, but have the water made
from the isotopes
18
O. After some time the
18
O isotope will be found (by means of a
Equilibria
mass spectrometer) in both
the ethanoic acid and the
water, but the concentrations
of the four substances will not
have changed.


Effect of changes in conditions on
position of equilibrium
• Le Chatelier’s principle may help you to
predict the direction of the change in the
position of equilibrium, but it does not
explain it.
• Temperature. An increase in temperature
will move the position of equilibrium in the
endothermic direction. Likewise a
decrease in temperature will move the
equilibrium in the exothermic direction:

Effect of changes in conditions on
position of equilibrium
As the reaction is exothermic left to right, an
increase in temperature will less ammonia to
be made, thus lowering the yield.
• Pressure. This applied only to reactions
involving gases. An increase in pressure
will drive the equilibrium to the side with
fewer gas molecules. Thus, for the
reaction above, an increase in pressure
will result in more ammonia in the
Effect of changes in conditions on
position of equilibrium
equilibrium mixture, i.e. an increased yield.
This is because there are only two gas
molecules on the right of the equation and
four on the left.
• Concentration. This applies to equilibrium
reactions in solution. If a substance is
physically or chemically removed from an
equilibrium system, the equilibrium will
shift to make more of that substance:
2CrO
4
2-
(aq) + 2H
+
(aq) Cr
2
O
7
2-
(aq) + H
2
O(l)
Effect of changes in conditions on
position of equilibrium
• Addition of alkali will remove the H+ ions,
causing the equilibrium to move to the left.
• Catalyst. This has no effect on the
position of equilibrium. What it does is to
increase the rate of reaching equilibrium,
thus a catalyst allows a reaction to be
carried out at a reasonable rate at a lower
temperature.
Optimum industrial conditions
Temperature
• Many industrial reactions, such as the
Haber process for manufacturing
ammonia, are reversible and exothermic.
For such reactions:
• If a high temperature is used, the yield at
equilibrium is small, but the rate of
reaction is fast.
Optimum industrial conditions
If a low temperature is used, the theoretical
yield is higher, but the rate of reaction is
slow.
• In a system such as this, a catalyst is used
to allow the reaction to proceed rapidly at
a temperature at which the yield is
reasonably good. This is often called a
compromise temperature, balancing yield
with rate. Any unreacted gases are then separated from
the products and recycled back through the catalyst
chamber.

Optimum industrial conditions
Pressure
• High pressures are extremely expensive,
and are only used if the yield at lower
pressures is too small to be economic.
• Two examples of manufacturing
processes that use very high pressures
are the Haber process and the
polymerization of ethene.

Things to learn
Things to learn
• An equilibrium constant expressed in
terms of concentration only applied when
all the reactants and products are in the
same phase – e.g a mixture of liquids or
gases. This is usually involves only
homogeneous equilibria.
• Partial pressure of a gas is the pressure
that the gas would have if it is occupied
the volume alone.

Things to learn
Things to learn
Manufacture of methanol
Manufacture of methanol
• There is an increase in entropy in the
forward reaction because there are more
gaseous molecules on the right-hand side.
• Notice that there are 2 moles of gas on the
right-hand side but only 1 mole of gas on
the left-hand side. So low pressure is
required to shift reaction more in the right
side.
Things to learn
• An endothermic reaction with an
increase in entropy is only
spontaneous at high temperature.
• An exothermic reaction with a
decrease in entropy suggests that
this reaction is spontaneous only
at low temperatures.

Controlling reactions for safety,
yield, cost and atom economy