Changes to Equilibrium

• Explain using Collision Theory

(concentration changes/temperature)
• Predict using Le Chatelier’s Principle
 System at equilibrium Changes to the system:
• Temperature 
• Adding more Volume/pressure 
• Concentration 
Affects the concentration reactants/products
of one or more
reactants/products

Change in rate of either

forward or reverse

Out of equilibrium
(temporarily)

Equilibrium re-established
 Change in Concentration (Partial Pressure)
Increasing the concentration of one the reactants would
• provide more particles
• resulting in more collisions
• temporarily favouring the forward rate and
• Producing more products which will increase the reverse rate until
• Both rates become equal again and
• System returns to a new equilibrium

Example 1
Can you explain all that is happening in this graph?

H2(g) + I2(g) HI(g)

 Example 2
Change in Concentration
The reaction between carbon dioxide and chlorine gases to produce
phosgene gas.

CO(g) + Cl2 (g) COCl2(g)

Adding chlorine to the system increases the concentration of chlorine.

CO(g) + Cl2 (g) COCl2(g)

Forward reaction is favoured as there are:

• more reactant particles,
• more collisions,
• greater chance of successful collision.

At equilibrium #2 there are more Cl2 and COCl2 molecules and less CO
molecules than at equilibrium #1
CO(g) + Cl2 (g)  COCl2(g)

Cl2 System again

Added at Equilibrium

Time
Concentration changes during the disruption to equilibrium.

[Cl2]

Cl2

CO

COCl2

Cl2
added
Example 3
Rate

COCl2 System again at

added equilibrium
Time
Concetration

COCl2 System again at

added equilibrium
Time
Changes to Temperature
The equilibrium constant, K, is affected by temperature. This means that the
concentrations of the reactants and product will be different at different
temperatures.

This can be explained using the collision theory and predicted by considering
the enthalpy changes for the forward and reverse reactions
When the temperature of a system is increased, the rate of both the
forward and reverse reactions will increase.

However, the rate of the endothermic reaction will increase more. This
is because due to the higher activation energy, the increase in
temperature will affect the percentage of particles able to react in the
endothermic reaction more than the exothermic reaction.

As more of the products of the endothermic reaction are produced, the

opposite, exothermic reaction rate will increase.

At the same time the endothermic reaction will decrease as the

reactants are used up.

This trend will continue until the two rates are once again equal and the
system is at equilibrium.
Consider the following reaction:

(a) Is this reaction endothermic or exothermic? _______________________

 
(b) Which reaction, forward or reverse, will increase more if the temperature
is increased?
 
______________________
 
(c) Will K be higher or lower at the higher temperature? Why?
 
___________________________________________________________
SO3

SO2

O2
Consider the following reaction:
The opposite trend occurs when the temperature decreases.

Explain the changes to rates and concentrations for this system when the
temperature decreases.
Summary
The effect of various changes on a chemical equilibrium system
can be predicted using Le Chatelier’s principle:

“If a system at equilibrium is subjected to a change in

conditions, the system will adjust to re-establish
equilibrium in such a way as to partially counteract
(oppose) the imposed change”
• A change a imposed to the system
• Forward/reverse rate favoured to
oppose the change until
• Equilibrium re-establish
• Concentration of reactants and
products are constant but different to
the concentrations at the original
equilibrium
 Example 2
Change in Concentration
The reaction between carbon dioxide and chlorine gases to produce
phosgene gas.

CO(g) + Cl2 (g) COCl2(g)

Adding chlorine to the system increases the concentration of chlorine.

CO(g) + Cl2 (g) COCl2(g)

Forward reaction is favoured (products increase) to oppose the increase of

chlorine until equilibrium is re-established.

At equilibrium #2 there are more Cl2 and COCl2 molecules and less CO
molecules than at equilibrium #1
CO(g) + Cl2 (g)  COCl2(g)

Cl2 System again

Added at Equilibrium

Time
Concentration changes during the disruption to equilibrium.

[Cl2]

Cl2

CO

COCl2

Cl2
added
Change in volume (or pressure of a gaseous system)

If the volume of a gaseous system, or the volume of the

solvent in a solution equilibrium system, is changed then
the concentrations making up that system will also be
changed.
Increasing the volume decreases the concentration

Decreasing the volume increases the concentration.

However…..
When the reaction contains equal numbers of particles on both sides of
the equation,

H2(g) + Cl2(g)  2HCl(g)

Then the systems will not be put out of equilibrium.

When a reaction has different numbers of particles on both sides of
the equation,

NO(g) + Cl2(g)  NOCl2(g)

Then the system will be put out of equilibrium by a change in volume

Increasing the volume decreases the Decreasing the volume increases

pressure. the pressure.

The rate of the reaction that increases The rate which decreases the
the number of gas particles will be number of particles will be
favoured. favoured
Volume of the 4 particles 2 particles
system is doubled

Pressure is halved

Reverse rate initially facoured

Different numbers of particles…..

Increasing the pressure favours (shifts towards) the side of the

equilibrium reaction with fewer moles of gas.
Less gas mean less pressure, ie partially counteracting the imposed
change
2 moles 1 mole
NO(g) + Cl2(g)  NOCl2(g)

The system is ‘trying’ to reduce the pressure by reducing the number of

particles.
Decreasing the pressure favours (shifts towards) the side of the
equilibrium reaction with the greater moles of gas.
More gas mean more pressure, ie partially counteracting the
imposed change

NO(g) + Cl2(g)  NOCl2(g)

The system is ‘trying’ to increase the pressure by increasing the number of

particles.
 NO(g) + Cl2(g)  NOCl2(g)
Concentration

Pressure System again at

increased equilibrium
Time
 NO(g) + Cl2(g)  NOCl2(g)
Concentration

Pressure System again at

decreased equilibrium
Time
No change to equilibrium if….

Both sides of the equilibrium

reaction have the same number of
moles of gas.

An inert gas (such as Argon) is added

Remember…
For gases

Increasing the volume decreases the pressure of a system.

Decreasing the volume increases the pressure of a system.

Macroscopic properties
Change in Temperature
To predict the effect of changing the temperature on an
equilibrium system, knowledge of the heat of reaction of
the system is required.

If ΔH is negative If ΔH is positive
the reaction is exothermic and the reaction is endothermic and
heat is one of the products. heat is one of the reactants.
If the temperature of an If the temperature of
equilibrium system is an equilibrium system
decreased is increased

Heat is removed Heat is added

The exothermic The endothermic

reaction is favoured reaction is favoured

To ‘try’ and increase To ‘try’ and decrease the

the temperature temperature
 If the temperature of the system at
equilibrium is changed, the value of the
equilibrium constant (K) will also be
changed.

Exothermic reactions Endothermic reactions

 Temperature K value  Temperature  K value
 Temperature K value  Temperature  K value
Addition of a Catalyst

Lowers activation energies for both the forward and reverse

reactions

Increases the rate of both the forward and reverse reactions

Does NOT affect the relative proportions of reactants and products

but does allow equilibrium to be reached more quickly.

Addition of a catalyst to a system at equilibrium has

NO EFFECT on the equilibrium concentration.
The addition or removal of reactants or products which
are present in the solid phase (s) or liquid phase (l), will
NOT ALTER the equilibrium concentrations.