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.