EQUILIBRIUM CONSTANTS: K

p
This page explains equilibrium constants expressed in terms of partial
pressures of gases, K
p
. It covers an explanation of the terms mole
fraction and partial pressure, and looks at K
p
for both homogeneous and
heterogeneous reactions involving gases.
Defning 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 x
A
. The mole
fraction of gas B would be x
B
- 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 P
A
. The partial
pressure of gas B would be P
B
- and so on.
There are two important relationships involving partial pressures. The
frst 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:
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).
K
p
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 K
p
, 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 K
p
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, K
p
.
Just like K
c
, K
p
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.
K
p
has exactly the same format as K
c
, 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.
The Contact Process equilibrium
You will remember that the equation for this is:
K
p
is given by:
The Haber Process equilibrium
The equation for this is:
. . . and the K
p
expression is:
K
p
in heterogeneous equilibria
A typical example of a heterogeneous equilibrium will involve gases in
contact with solids.
Writing an expression for K
p
for a heterogeneous equilibrium
Exactly as happens with K
c
, you don't include any term for a solid in the
equilibrium expression.
The next two examples have already appeared on the K
c
page.
The equilibrium produced on heating carbon with steam
Everything is exactly the same as before in the expression for K
p
, except
that you leave out the solid carbon.
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.
.
EQUILIBRIUM CONSTANTS and LE
CHATELIER'S PRINCIPLE
This page looks at the relationship between equilibrium constants
and Le Chatelier's Principle. Students often get confused about
how it is possible for the position of equilibrium to change as you
change the conditions of a reaction, although the equilibrium
constant may remain the same.
Be warned that this page assumes a good understanding of Le
Chatelier's Principle and how to write expressions for equilibrium
constants.
Changing concentrations
The facts
Equilibrium constants aren't changed if you change the
concentrations of things present in the equilibrium. The only thing
that changes an equilibrium constant is a change of temperature.
The position of equilibrium is changed if you change the
concentration of something present in the mixture. According to Le
Chatelier's Principle, the position of equilibrium moves in such a
way as to tend to undo the change that you have made.
Suppose you have an equilibrium established between four
substances A, B, C and D.
According to Le Chatelier's Principle, if you decrease the
concentration of C, for example, the position of equilibrium will
move to the right to increase the concentration again.
Note: The reason for choosing an equation with "2B" will
become clearer when I deal with the efect of pressure further
down the page.
Explanation in terms of the constancy of the equilibrium
constant
The equilibrium constant, K
c
for this reaction looks like this:
If you have moved the position of the equilibrium to the right (and
so increased the amount of C and D), why hasn't the equilibrium
constant increased?
This is actually the wrong question to ask! We need to look at it the
other way round.
Let's assume that the equilibrium constant mustn't change if you
decrease the concentration of C - because equilibrium constants
are constant at constant temperature. Why does the position of
equilibrium move as it does?
If you decrease the concentration of C, the top of the K
c
expression
gets smaller. That would change the value of K
c
. In order for that
not to happen, the concentrations of C and D will have to increase
again, and those of A and B must decrease. That happens until a
new balance is reached when the value of the equilibrium constant
expression reverts to what it was before.
The position of equilibrium moves - not because Le Chatelier says
it must - but because of the need to keep a constant value for the
equilibrium constant.
If you decrease the concentration of C:
Changing pressure
This only applies to systems involving at least one gas.
The facts
Equilibrium constants aren't changed if you change the pressure
of the system. The only thing that changes an equilibrium constant
is a change of temperature.
The position of equilibrium may be changed if you change the
pressure. According to Le Chatelier's Principle, the position of
equilibrium moves in such a way as to tend to undo the change that
you have made.
That means that if you increase the pressure, the position of
equilibrium will move in such a way as to decrease the pressure
again - if that is possible. It can do this by favouring the reaction
which produces the fewer molecules. If there are the same number
of molecules on each side of the equation, then a change of
pressure makes no diference to the position of equilibrium.
Explanation
Where there are diferent numbers of molecules on each side
of the equation
Let's look at the same equilibrium we've used before. This one
would be afected by pressure because there are 3 molecules on
the left but only 2 on the right. An increase in pressure would move
the position of equilibrium to the right.
Because this is an all-gas equilibriium, it is much easier to use K
p
:
Once again, it is easy to suppose that, because the position of
equilibrium will move to the right if you increase the pressure, K
p

will increase as well. Not so!
To understand why, you need to modify the K
p
expression.
Remember the relationship between partial pressure, mole fraction
and total pressure?
Note: If you aren't happy with this, read the beginning of the
page about K
p
before you go on.
Use the BACK button on your browser to return to this page.
Replacing all the partial pressure terms by mole fractions and total
pressure gives you this:
If you sort this out, most of the "P"s cancel out - but one is left at
the bottom of the expression.
Now, remember that K
p
has got to stay constant because the
temperature is unchanged. How can that happen if you increase P?
To compensate, you would have to increase the terms on the top,
x
C
and x
D
, and decrease the terms on the bottom, x
A
and x
B
.
Increasing the terms on the top means that you have increased the
mole fractions of the molecules on the right-hand side. Decreasing
the terms on the bottom means that you have decreased the mole
fractions of the molecules on the left.
That is another way of saying that the position of equilibrium has
moved to the right - exactly what Le Chatelier's Principle predicts.
The position of equilibrium moves so that the value of K
p
is kept
constant.
Where there are the same numbers of molecules on each side
of the equation
In this case, the position of equilibrium isn't afected by a change of
pressure. Why not?
Let's go through the same process as before:
Substituting mole fractions and total pressure:
. . . and cancelling out as far as possible:
There isn't a single "P" left in the expression. Changing the
pressure can't make any diference to the K
p
expression. The
position of equilibrium doesn't need to move to keep K
p
constant.
Changing temperature
The facts
Equilibrium constants are changed if you change the temperature
of the system. K
c
or K
p
are constant at constant temperature, but
they vary as the temperature changes.
Look at the equilibrium involving hydrogen, iodine and hydrogen
iodide:
The K
p
expression is:
Two values for K
p
are:
temperature K
p
500 K 160
700 K 54
You can see that as the temperature increases, the value of K
p

falls.
Note: You might possibly be wondering what the units of K
p

are. This particular example was chosen because in this case,
K
p
doesn't have any units. It is just a number.
The units for equilibrium constants vary from case to case. It is
much easier to understand this from a book than from a lot of
maths on screen. You will fnd this explained in my chemistry
calculations book.
This is typical of what happens with any equilibrium where the
forward reaction is exothermic. Increasing the temperature
decreases the value of the equilibrium constant.
Where the forward reaction is endothermic, increasing the
temperature increases the value of the equilibrium constant.
Note: Any explanation for this needs knowledge beyond the
scope of any UK A level (or equivalent) syllabus.
The position of equilibrium also changes if you change the
temperature. According to Le Chatelier's Principle, the position of
equilibrium moves in such a way as to tend to undo the change that
you have made.
If you increase the temperature, the position of equilibrium will
move in such a way as to reduce the temperature again. It will do
that by favouring the reaction which absorbs heat.
In the equilibrium we've just looked at, that will be the back reaction
because the forward reaction is exothermic.
So, according to Le Chatelier's Principle the position of equilibrium
will move to the left. Less hydrogen iodide will be formed, and the
equilibrium mixture will contain more unreacted hydrogen and
iodine.
That is entirely consistent with a fall in the value of the equilibrium
constant.
Adding a catalyst
The facts
Equilibrium constants aren't changed if you add (or change) a
catalyst. The only thing that changes an equilibrium constant is a
change of temperature.
The position of equilibrium is not changed if you add (or change)
a catalyst.
Explanation
A catalyst speeds up both the forward and back reactions by
exactly the same amount. Dynamic equilibrium is established when
the rates of the forward and back reactions become equal. If a
catalyst speeds up both reactions to the same extent, then they will
remain equal without any need for a shift in position of equilibrium.
Note: If you know about the Arrhenius equation, it isn't too
difcult to use it to show that the ratio of the rate constants for
the forward and back reactions isn't afected by adding a
catalyst. Although the activation energies for the two reactions
change when you add a catalyst, they both change by the same
amount.
I'm not going to do this bit of algebra, because it would never
be asked at this level (UK A level or equivalent).