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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.
Important: If you aren't happy about the basics of
equilibrium, explore the equilibrium menu before you waste
your time on this page.
This page should only be read when you are confident about
everything else to do with equilibria.

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 effect of pressure further
down the page.

Explanation in terms of the constancy of the equilibrium


constant
The equilibrium constant, Kc 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
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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 Kc
expression gets smaller. That would change the value of Kc. 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 difference to the position of equilibrium.

Explanation
Where there are different numbers of molecules on each side
of the equation
Let's look at the same equilibrium we've used before. This one
would be affected 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 Kp:

Once again, it is easy to suppose that, because the position of

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equilibrium will move to the right if you increase the pressure, Kp


will increase as well. Not so!
To understand why, you need to modify the Kp 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 Kp 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 Kp 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,
xC and xD, and decrease the terms on the bottom, xA and xB.
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 Kp 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 affected 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:

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There isn't a single "P" left in the expression. Changing the


pressure can't make any difference to the Kp expression. The
position of equilibrium doesn't need to move to keep Kp constant.

Changing temperature
The facts
Equilibrium constants are changed if you change the
temperature of the system. Kc or Kp are constant at constant
temperature, but they vary as the temperature changes.
Look at the equilibrium involving hydrogen, iodine and hydrogen
iodide:

The Kp expression is:

Two values for Kp are:

temperature

Kp

500 K

160

700 K

54

You can see that as the temperature increases, the value of Kp


falls.

Note: You might possibly be wondering what the units of Kp


are. This particular example was chosen because in this
case, Kp 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 find 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.

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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


difficult to use it to show that the ratio of the rate constants
for the forward and back reactions isn't affected 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).

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Exploring some of this using a simple computer


program
The link below will take you to a page where you can explore the
effect of changing conditions on the reaction:

The page comes from Davidson College in America. It needs you


to have Java enabled in your browser.
Note: If this link stops working, please let me know using
the address on the about this site page. If your browser
doesn't have Java enabled, then you won't see the important
part of the page, and you will have to enable Java. I'm afraid
that is your problem - it varies from browser to browser. You
could try reading this page about enabling Java.

You are told that the reaction is endothermic, and can change
things like the temperature, the volume of the mixture, and the
amounts of all the reactants to see what would happen.
It would be best if you worked out what you expected to happen
before you change anything. You change things by moving the grey
sliders.
You will notice that there is no direct way of changing the pressure.
Instead, you have to change the volume. Obviously, if you decrease
the volume, keeping the amounts of everything constant, that
increases the pressure.
If you do this to change the pressure, concentrate on the red bars
showing what happens to the number of moles of substances
present. The blue bars are more confusing. These represent
concentrations, and these will change not only because of the
change in quantities present, but also because of the change in
volume. That's confusing!

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 equilibrium constants and Le Chatelier's Principle
answers

Where would you like to go now?


To the equilibrium menu . . .
To the Physical Chemistry menu . . .
To Main Menu . . .

Jim Clark 2002 (last modified May 2013)

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