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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.
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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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.
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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.
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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:
temperature
Kp
500 K
160
700 K
54
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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.
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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!
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