Equilibrium part 2

Le Chateliers Principle

The main part of this topic is learning how to use Le Chateliers principle. We looked at the position of
equilibrium in part 1. Le Chateliers principle allows you to predict what happens to the position of
equilibrium when the conditions change.

The principle:

with any change in temperature, pressure or concentration, the system will try to counteract the
change by moving the equilibrium position in the opposite direction.

This principle is quite counter-intuitive and not easy to understand at first.

So what happens?

The system will happily remain in is equilibrium unless a change is made. So when there is a change in the
conditions, the system is briefly knocked out of equilibrium.

For example, if you increase the temperature, the system now has too much heat and will try to
remove this extra heat. In doing so, the position of equilibrium is changed and the system now has a new
equilibrium position and a different amount of products and reactants being made.

Its actually a lot easier to do the questions than to understand this fully.

Concentration

Looking at the Haber process again:

If the concentration of N2 or H2 is increased, the equilibrium position will move to the right. Or if the
concentration of N2 or H2 is decreased the equilibrium position moves to the left.

Why? This is all about trying to counteract the changes in concentration. By increasing the
concentrations, we now have too much N2 or H2. The system moves to the right where there is no N2 or
H2 to try to remove this excess and in the process it makes more NH3.

And you just need to reverse the argument for decreasing the concentrations. By decreasing the
concentrations, there is less N2 or H2 on the left hand side. The system tries to make more N2 or H2 to
balance it out again by shifting the equilibrium position to the left.
You can do the same with NH3. Increasing the concentration of NH3 moves the equilibrium to the left to
balance out the excess. Decreasing the concentration of NH3 moves the equilibrium shifts to the right to
make more of it.

Pressure

Pressure is only for gases. We will use the same example again (they are all in the gaseous state):

The easiest way to look at changes in pressure is to count the number of moles on each side of the
equation:

Left hand side: 1 x N2 and 3 x H2 4 moles

Right hand side: 2 x NH3 2 moles

Therefore we can say that the left side is the high pressure side and the right side is the low pressure
side.

With concentration we talked about changing the concentration of individual reactants or products.
With pressure (and temperature) this doesnt happen, it is a general change for the whole system.

If the pressure is increased, the equilibrium moves to the side with fewer moles and vice-versa. So in
the example above, an increase in pressure will shift the equilibrium to make more NH 3.

Sometimes an equation will have a solid in it, you have to ignore it when counting up the number of
moles.

Also, if the number of moles is the same on each side then changes in pressure will have no effect.

Temperature

If there is an increase in temperature, the system will try to remove this excess heat.

you must know if the reaction is exothermic or endothermic

Again for the Haber process:

From the negative enthalpy value, we can see that the forward reaction is exothermic.

If the forward reaction is exothermic, then the backward reaction is endothermic.

Exothermic means that heat is given out. So if we decrease the temperature the equilibrium shifts to the
right as the system is giving out heat, which will balance out the decrease.

If we increase the temperature, the equilibrium moves in the direction where heat is taken in to balance
it out.

A decrease in temperature means that the equilibrium goes in the exothermic direction. An increase
in temperature means that the equilibrium goes in the endothermic direction.

Catalysts
They often ask about the effect of a catalyst on equilibrium:

catalysts have no affect on the equilibrium position

A catalyst just speeds up a reaction, meaning you get to equilibrium quicker but does not affect the
amount of products made.

Industrial Processes
The same principles that we have looked at still apply here. As we are looking at industrial processes, you
have to talk about two factors: cost and speed.

For example, the good old Haber process yet again:

They are trying to make ammonia, so ideally they want the equilibrium to lie as far to the right as far as
possible to get a high yield. From Le Chateliers principle, this would mean high pressure and low
temperature.

Buta low temperature is going to be too slow (see the rates topic for more on this) and high pressure is
expensive as they have to build very strong pipes.

So they have to reach a compromise. The reaction has to use a high enough temperature to make it
reasonably fast but not too high a temperature that it gives a poor yield.
Similarly with pressure, a high enough pressure is needed to force the equilibrium to the right but not too
high that it is going to cost a fortune.

Remember the word compromise.

The Equilibrium Constant, Kc

So far we have talked a lot about the position of equilibrium either lying to the left or right. This is quite
vague. To make it a bit more exact we can use something called the equilibrium constant, Kc (c for
concentration).

Kc is just a number that gives a better indication of where the equilibrium position is.

Writing the Kc expression

Kc is just the concentrations of the products divided by the concentrations of the reactants. Also need to
use the number of moles in the chemical equation and put them as powers:

To demonstrate this here are a couple of examples:

 Note the square brackets [ ] which are used for concentrations.

Calculating Kc

This should be easy. All you have to do is put the numbers into the K c expression.

If Kc > 1 then the equilibrium lies to the right

If Kc < 1 then the equilibrium lies to the left

The greater the value (above 1) then the further to the right the equilibrium lies and the more products
that are being made.