EQUILIBRIUM CONSTANTS: Kc

This page explains what is meant by an equilibrium constant,

introducing equilibrium constants expressed in terms of
concentrations, Kc. It assumes that you are familiar with the
concept of a dynamic equilibrium, and know what is meant by the
terms "homogeneous" and "heterogeneous" as applied to
chemical reactions.
Important: If you aren't sure about dynamic equilibria it is
important that you follow this link before you go on.
If you aren't sure what homogeneous and heterogeneous
mean, you would find it useful to follow this link and read the
beginning of the page that you will find (actually on catalysis).
Use the BACK button on your browser to return to this page.

We need to look at two different types of equilibria (homogeneous

and heterogeneous) separately, because the equilibrium constants
are defined differently.
A homogeneous equilibrium has everything present in the
same phase. The usual examples include reactions where
everything is a gas, or everything is present in the same
solution.
A heterogeneous equilibrium has things present in more
than one phase. The usual examples include reactions
involving solids and gases, or solids and liquids.

Kc in homogeneous equilibria
This is the more straightforward case. It applies where everything
in the equilibrium mixture is present as a gas, or everything is
present in the same solution.
A good example of a gaseous homogeneous equilibrium is the
conversion of sulphur dioxide to sulphur trioxide at the heart of the
Contact Process:

A commonly used liquid example is the esterification reaction

between an organic acid and an alcohol - for example:

Writing an expression for Kc

We are going to look at a general case with the equation:

No state symbols have been given, but they will be all (g), or all (l),
or all (aq) if the reaction was between substances in solution in
water.
If you allow this reaction to reach equilibrium and then measure the
equilibrium concentrations of everything, you can combine these
concentrations into an expression known as an equilibrium
constant.
The equilibrium constant always has the same value (provided you
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don't change the temperature), irrespective of the amounts of A, B,

C and D you started with. It is also unaffected by a change in
pressure or whether or not you are using a catalyst.

Compare this with the chemical equation for the equilibrium. The
convention is that the substances on the right-hand side of the
equation are written at the top of the Kc expression, and those on
the left-hand side at the bottom.
The indices (the powers that you have to raise the concentrations
to - for example, squared or cubed or whatever) are just the
numbers that appear in the equation.
Note: If you have come across orders of reaction, don't
confuse this with the powers that appear in the rate equation
for a reaction. Those powers (the order of the reaction with
respect to each of the reactants) are experimentally
determined. They don't have any direct connection with the
numbers that appear in the equation
You may come across attempts to derive the expression for
Kc by writing rate equations for the forward and back
reactions. Except in a very limited number of very simple
examples, this can't be done! These attempts make the
fundamental mistake of obtaining the rate equation from the
chemical equation. That's WRONG! Deriving an expression
for Kc is impossible at this level of chemistry.
It isn't relevant to this page, but if you want to find out more
about orders of reaction, you might like to follow this link at
some time in the future.

Some specific examples

The esterification reaction equilibrium
A typical equation might be:

There is only one molecule of everything shown in the equation.

That means that all the powers in the equilibrium constant
expression are "1". You don't need to write those into the Kc
expression.

As long as you keep the temperature the same, whatever

proportions of acid and alcohol you mix together, once equilibrium
is reached, Kc always has the same value. At room temperature,
this value is approximately 4 for this reaction.

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The equilibrium in the hydrolysis of esters

This is the reverse of the last reaction:

The Kc expression is:

If you compare this with the previous example, you will see that all
that has happened is that the expression has turned upside-down.
Its value at room temperature will be approximately 1/4 (0.25).
It is really important to write down the equilibrium reaction
whenever you talk about an equilibrium constant. That is the only
way that you can be sure that you have got the expression the right
way up - with the right-hand substances on the top and the lefthand ones at the bottom.
The Contact Process equilibrium
You will remember that the equation for this is:

This time the Kc expression will include some visible powers:

Although everything is present as a gas, you still measure

concentrations in mol dm-3. There is another equilibrium constant
called Kp which is more frequently used for gases. You will find a
link to that at the bottom of the page.
The Haber Process equilibrium
The equation for this is:

. . . and the Kc expression is:

Kc in heterogeneous equilibria
Typical examples of a heterogeneous equilibrium include:
The equilibrium established if steam is in contact with red hot
carbon. Here we have gases in contact with a solid.

If you shake copper with silver nitrate solution, you get this
equilibrium involving solids and aqueous ions:

Writing an expression for Kc for a heterogeneous

equilibrium
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The important difference this time is that you don't include any

term for a solid in the equilibrium expression.

Taking another look at the two examples above, and adding a third
one:
The equilibrium produced on heating carbon with steam

Everything is exactly the same as before in the equilibrium

constant expression, except that you leave out the solid carbon.

The equilibrium produced between copper and silver ions

Both the copper on the left-hand side and the silver on the right are
solids. Both are left out of the equilibrium constant expression.

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 Kc
There are all sorts of calculations you might be expected to do
which are centred around equilibrium constants. You might be
expected to calculate a value for Kc including its units (which vary
from case to case). Alternatively you might have to calculate
equilibrium concentrations from a given value of Kc and given
starting concentrations.
This is simply too huge a topic to be able to deal with satisfactorily
on the internet. It isn't the best medium for learning how to do
chemistry calculations. It is much easier to do this from a carefully
structured book giving you lots of worked examples and lots of
problems to try yourself.
If you have found this site useful, you might like to have a look at my
book on chemistry calculations. It covers equilibrium constant
calculations starting with the most trivial cases, and gradually
getting harder - up to the moderately difficult examples which may
be asked in a UK A' level examination.

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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 Kc
answers

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To look at Kp . . .
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Jim Clark 2002 (modified May 2013)

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