EQUILIBRIUM CONSTANTS: Kp

This page explains equilibrium constants expressed in terms of

partial pressures of gases, Kp. It covers an explanation of the
terms mole fraction and partial pressure, and looks at Kp for both
homogeneous and heterogeneous reactions involving gases.
The page assumes that you are already familiar with the concept
of an equilibrium constant, and that you know about Kc - an
equilibrium constant expressed in terms of concentrations
Important: If you have come directly to this page via a
search engine, you should first read the page on equilibrium
constants - Kc before you go on - unless you are already fully
confident about how to write expressions for Kc.
You will find a link back to this page at the bottom of the Kc
page.

Defining some terms

Before we can go any further, there are two terms relating to
mixtures of gases that you need to be familiar with.

Mole fraction
If you have a mixture of gases (A, B, C, etc), then the mole fraction
of gas A is worked out by dividing the number of moles of A by the
total number of moles of gas.
The mole fraction of gas A is often given the symbol xA. The mole
fraction of gas B would be xB - and so on.

Pretty obvious really!

For example, in a mixture of 1 mole of nitrogen and 3 moles of
hydrogen, there are a total of 4 moles of gas. The mole fraction of
nitrogen is 1/4 (0.25) and of hydrogen is 3/4 (0.75).

Partial pressure
The partial pressure of one of the gases in a mixture is the
pressure which it would exert if it alone occupied the whole
container.
The partial pressure of gas A is often given the symbol PA. The
partial pressure of gas B would be PB - and so on.
There are two important relationships involving partial pressures.
The first is again fairly obvious.
The total pressure of a mixture of gases is equal to the sum of the
partial pressures.

It is easy to see this visually:

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Gas A is creating a pressure (its partial pressure) when its

molecules hit the walls of its container. Gas B does the same.
When you mix them up, they just go on doing what they were doing
before. The total pressure is due to both molecules hitting the walls
- in other words, the sum of the partial pressures.
The more important relationship is the second one:

Learn it!
That means that if you had a mixture made up of 20 moles of
nitrogen, 60 moles of hydrogen and 20 moles of ammonia (a total
of 100 moles of gases) at 200 atmospheres pressure, the partial
pressures would be calculated like this:

gas

mole fraction

partial pressure

nitrogen

20/100 = 0.2

0.2 x 200 = 40 atm

hydrogen

60/100 = 0.6

0.6 x 200 = 120 atm

ammonia

20/100 = 0.2

0.2 x 200 = 40 atm

Partial pressures can be quoted in any normal pressure units. The

common ones are atmospheres or pascals (Pa). Pascals are
exactly the same as N m-2 (newtons per square metre).

Kp in homogeneous gaseous equilibria

A homogeneous equilibrium is one in which everything in the
equilibrium mixture is present in the same phase. In this case, to
use Kp, everything must be a gas.
A good example of a gaseous homogeneous equilibrium is the
conversion of sulphur dioxide to sulphur trioxide at the heart of the
Contact Process:

Writing an expression for Kp

We are going to start by looking at a general case with the
equation:

If you allow this reaction to reach equilibrium and then measure (or
work out) the equilibrium partial pressures of everything, you can
combine these into the equilibrium constant, Kp.
Just like Kc, Kp always has the same value (provided you don't
change the temperature), irrespective of the amounts of A, B, C
and D you started with.

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Kp has exactly the same format as Kc, except that partial

pressures are used instead of concentrations. The gases on the
right-hand side of the chemical equation are at the top of the
expression, and those on the left at the bottom.
Beware! People are sometimes tempted to write brackets
around the individual partial pressure terms. Don't do it! Even
if you intend to write normal round brackets, it is too easy in
an exam to write them as square brackets instead. This
makes it look as if you are confusing Kp with Kc. Examiners
don't like it, and you could be penalised.

The Contact Process equilibrium

You will remember that the equation for this is:

Kp is given by:

The Haber Process equilibrium

The equation for this is:

. . . and the Kp expression is:

Kp in heterogeneous equilibria
A typical example of a heterogeneous equilibrium will involve
gases in contact with solids.

Writing an expression for Kp for a heterogeneous

equilibrium
Exactly as happens with Kc, you don't include any term for a solid

in the equilibrium expression.

The next two examples have already appeared on the Kc page.
The equilibrium produced on heating carbon with steam

Everything is exactly the same as before in the expression for Kp,

except that you leave out the solid carbon.

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The equilibrium produced on heating calcium carbonate

This equilibrium is only established if the calcium carbonate is
heated in a closed system, preventing the carbon dioxide from
escaping.

The only thing in this equilibrium which isn't a solid is the carbon
dioxide. That is all that is left in the equilibrium constant
expression.

Calculations involving Kp
On the Kc page, I've already discussed the fact that the internet
isn't a good medium for learning how to do calculations.
If you want lots of worked examples and problems to do yourself
centred around Kp, you might be interested in my book on
chemistry calculations.

Note: If you are interested in my chemistry calculations

book you might like to follow this link.

Questions to test your understanding

If this is the first set of questions you have done, please read the
introductory page before you start. You will need to use the BACK BUTTON
on your browser to come back here afterwards.
questions on Kp
answers

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Jim Clark 2002 (modified May 2013)

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