Position of Equilibrium

Equilibrium
Equilibrium is a state of balance in which nothing changes.

However, the system is dynamic, i.e. in constant motion.
As fast as the reactants are converted into products, the products are being converted back
into reactants.
The forward reaction is the same as the back reaction.
A chemical system is in dynamic equilibrium when:
The concentrations of the reactants and the products remain the same
The rate of the forward reaction is the same as the rate of the reverse reaction
If the backward reaction is significant then the reaction is reversible.
Position of Equilibrium
There are many equilibrium mixtures possible for a given reaction system, depending on the
concentrations of the substances you mix and the conditions such as temperature and
pressure.
We often use the term position of equilibrium to describe one set of equilibrium
concentrations for a reaction.
If one of the concentrations is changed then the system is no longer in equilibrium, and the
concentrations of all the substances will change until a new position of equilibrium is
reached.
If most of the reactants become products before the reverse reaction increases sufficiently
to establish equilibrium, we say that the position of equilibrium lies to the right the
products.
If little of the reactants have changed to products when the reverse reaction becomes equal
to the rate of the forward reaction, we say that the position of equilibrium lies to the left.
Shifting the Position of Equilibrium

The position of an equilibrium can be altered by changing:
The concentrations of reacting substances if dealing with solutions

The pressure of reacting gases
The temperature
Le Chateliers Principal
If a system is at equilibrium and a change is made in any of the conditions, then the system
responds to counteract the change as much as possible.
Using Catalysts
Using a catalyst does not shift the position of equilibrium.
A catalyst lowers the activation enthalpy of a reaction.
As the reaction is reversible, the activation enthalpy of both the forward and reverse
reactions will be reduced by the same amount, so both will speed up by the same
proportion.
This means that the same equilibrium position is reached.
The catalyst causes the equilibrium position to be reached much more quickly than it would
if no catalyst were used.
Changing the Concentration

Concentration change
Increasing reactants
Equilibrium shift
To the right
What it does
Decreases reactants
Increasing products
To the left
Decreases products
Decreasing reactants
To the left
Increases reactants
Decreasing products
To the right
Increases products
Equilibrium shift
To the side with fewer gas
molecules
Example
CO (g) + 2H2 (g) = CH3OH (g)
3 molecules
1 molecule
Changing the Pressure

Pressure change
Increases
Moves to the right

Decreases
To the side with more gas

molecules
CH4 (g) + H2O (g) = CO (g) + 3H2 (g)

2 molecules
4 molecules
Moves to the right
Changing the Temperature

Temperature change
Increase
Equilibrium shift
Position of equilibrium shifts
in the direction of the
endothermic reaction
What it does
Adds heat
Decrease
Position of equilibrium shifts

in the direction of the
exothermic reaction
Removes heat
Linking Equilibria together

In many systems, particularly naturally occurring systems, two or more equilibria are linked
together so that the product of one equilibrium is the reactant in the second equilibrium.
This is the case for the two reversible reactions involving carbon dioxide.
CO2 (g) = CO2 (aq)
And
CO2 (aq) + H2O (l) = HCO3- (aq) + H+ (aq)
The product of the first equilibrium is a reactant in the second, so that the dissolved carbon
dioxide is involved in both equilibria.
Le Chateliers principal can be used to predict the effect of imposing a change on this
equilibrium system.
For example, if more gaseous carbon dioxide is added, the position of the first equilibrium
will move to the right and more CO 2 (aq) will be formed.
This increase in the concentration of CO 2 (aq) will then cause the position of the second
equilibrium to move to the right to produce more HCO 3- (aq) and H+ (aq).
Le Chateliers principle helps in the development of theories to explain naturally occurring

systems that involve reversible reactions, such as the dissolving of atmospheric carbon
dioxide in oceans.
Steady State Systems

A chemical equilibrium can only be established in a closed system which is sealed off from
its surroundings.
In an open system, a series of reactions can reach a steady state, where the concentrations
of reactants and products remain constant.
An example of a steady state is the production and destruction of ozone in the stratosphere:
Ozone production
O + O 2 O3
Ozone destruction
O3 O2 + O
O + O 3 O2 + O2
None of these reactions come to equilibrium, but left to themselves they will reach a point
where ozone is being produced as fast as it is being used up, so its concentration stays the
same the series has reached a steady state.

Position of Equilibrium

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Position of Equilibrium

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Equilibrium

Equilibrium is a state of balance in which nothing changes.

If the backward reaction is significant then the reaction is reversible.

Shifting the Position of Equilibrium

The concentrations of reacting substances if dealing with solutions

Changing the Concentration

Changing the Pressure

Moves to the right

To the side with more gas

CH4 (g) + H2O (g) = CO (g) + 3H2 (g)

Changing the Temperature

Position of equilibrium shifts

Linking Equilibria together

Le Chateliers principle helps in the development of theories to explain naturally occurring

Steady State Systems

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