Equilibria part 2

Kp
Kp is only for gases. In the same way as we wrote out Kc, we can write out a Kp expression:

The Kp expression is the same format as for Kc, but with curved brackets rather than square brackets. A
little p is used to show that it is pressure.

The p is called partial pressure, which we will look at below.

if any solids or liquids are in the chemical equation then you cannot include them in the Kp
expression.

Partial Pressure

the pressure a gas exerts on a container if it was in the container on its own

The word partial is used because there will be more than one gas in the reaction mixture and each gas
exerts part of the total pressure.

To do the calculations you need to know the partial pressures of each reactant and product using:

partial pressure = mole fraction x total pressure

Total Pressure
The total pressure is easy, either use this equation, or they give you the value in the question:

total pressure = sum of the partial pressures

Mole fraction

mole fraction = moles of a particular gas/moles of all the gases

Similar to what we did in the Kc part of this tutorial, we can use the ICE method to get the equilibrium
moles. As its the same method, we will assume we have the equilibrium moles and continue from there:

Equilibrium moles: 0.4 0.4 1.6 2.1

Mole Fractions:

CH4 = 0.4/0.4+0.4+1.6+2.1 = 0.4/4.5 = 0.089

H2O = 0.4/4.5 = 0.089

CO = 1.6/4.5 = 0.36

H2 = 2.1/4.5 = 0.47

the sum of the mole fractions always adds up to 1.

Calculating Kp
Still using the example above, the question gave the total pressure as 2 atm (atmospheres). As we know
this and have calculated the mole fractions, we can now calculate the partial pressures:

Partial Pressures:

CH4 = 0.089 x 2 = 0.178 atm

H2O = 0.089 x 2 = 0.178 atm

CO = 0.36 x 2 = 0.72 atm

H2 = 0.47 x 2 = 0.94 atm

Once you have the partial pressure values, you can put them straight into the Kp expression:
 Kp = (0.72) x (0.94)3/0.178 x 0.178

Kp = 0.598/0.032 = 18.7 atm2

Units

These are calculated the same as we did for Kc. Just put in atm as the units of pressure and cancel out
until you are left with atm2.

Further examples
In the question above we were given all the equilibrium moles. But if they dont give you them all, you
can use the same ICE method we looked at for the Kc calculation in part 1.

They might say something like 75% of the reactants have reacted. It feels like there is a lack of
information.

In this case you have to assume that the starting number of moles of each reactant is 1 (or 100%)

From this starting point we can now use the same theory as for the K c calculation. Just put the starting
number of moles of reactants as 1.

As 75% of the reactants have reacted, we can simply remove 0.75 from each of them to give 0.25. Then
similar to our Kc method, if 0.75 have reacted then 0.75 of the products must have formed (all 1:1 ratios
here):

Initial 1 1 0 0

Change -0.75 -0.75 +0.75 +0.75

Equilibrium 0.25 0.25 0.75 0.75

From there you can proceed as we did above by working out the mole fraction and using the total
pressure from the question to work out the partial pressures and then K p.

How does pressure affect Kp?

As we discussed in part 1 of this tutorial, only temperature affects K c or Kp. The explanation given in part
1 of this tutorial should be good enough. But to show where K p fits into all this, there is a bit more detail
below.
If we rewrite the Kp expression in terms of mole fractions it is actually easier to see what is going on:

We can then cancel the P symbols on top and bottom to leave only one remaining P on the top line:

Remember from part 1 we said that it is best to think of this in two parts:

1. the initial change

2. the equilibrium shifting

Initial: an increase in pressure will only affect the top line (as it has the P in it). The top line of the Kp
expression will increase in value and the system is out of equilibrium.

Equilibrium shift: as there are a different number of moles on each side of the equation (2 on the left and
4 on the right), an increase in pressure would move the equilibrium to the left (to recover the
equilibrium) and the bottom line would increase in value and eventually leads to Kp remaining constant.

in summary, answer the question in terms of mole fractions i.e. tell them that the mole fractions of
the reactants (in this case) must increase to keep Kp constant.

similarly, if you rewrote a Kp expression as we did above for an equation where the moles on the left
and right are the same, then you will find that all the P symbols cancel, therefore, pressure has no
effect.