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SOLUBILITY PRODUCT and THE

COMMON ION EFFECT

This page looks at the common ion effect related to solubility

products, including a simple calculation. You need to know about
solubility products and calculations involving them before you
read this page.

What is the common ion effect?

I need to look again at a simple solubility product calculation,

before we go on to the common ion effect.

The solubility of lead(II) chloride in water

Lead(II) chloride is sparingly soluble in water, and this

equilibrium is set up between the solid and its ions in solution:

If you just shook up some solid lead(II) chloride with water, then
the solution would obviously contain twice as many chloride ions
as lead(II) ions.

The expression for the solubility product and its value are given
by:

Note: I have no confidence in the accuracy of this value.

There are serious discrepancies between the values from

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different sources. But that makes no difference to the

discussion.

For comparison purposes later, I need to work out the lead(II)

ion concentration in this saturated solution.

If the concentration of dissolved lead(II) chloride is s mol dm-3,

then:

[Pb2+] = s mol dm-3

[Cl- ] = 2s mol dm-3

Put these values into the solubility product expression, and do

the sum.

So the concentration of lead(II) ions in the solution is 1.62 x 10-2

mol dm-3 (or 0.0162 mol dm-3 if you prefer).

What happens if you add some sodium chloride to this

saturated solution?

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Now we are ready to think about the common ion effect.

Sodium chloride shares an ion with lead(II) chloride. The

chloride ion is common to both of them. This is the origin of the
term "common ion effect".

Look at the original equilibrium expression again:

What would happen to that equilibrium if you added extra

chloride ions?

According to Le Chatelier, the position of equilibrium would shift

in order to counter what you have just done. In this case, it
would tend to remove the chloride ions by making extra solid
lead(II) chloride.

Note: Actually, of course, the concentration of lead(II) ions in

the solution is so small to start with, that only a tiny proportion
of the extra chloride ions can be converted into solid lead(II)
chloride.

The lead(II) chloride will become even less soluble - and, of

course, the concentration of lead(II) ions in the solution will
decrease.

Something similar happens whenever you have a sparingly

soluble substance. It will be less soluble in a solution which
contains any ion which it has in common. This is the common
ion effect.

A simple calculation to show this

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Suppose you tried to dissolve some lead(II) chloride in some

0.100 mol dm-3 sodium chloride solution instead of in water.
What would the concentration of the lead(II) ions be this time?

As before, let's call the concentration of the lead(II) ions s.

[Pb2+] = s mol dm-3

Now the sum gets different. This time the concentration of the
chloride ions is governed by the concentration of the sodium
chloride solution. The number of ions coming from the lead(II)
chloride is going to be tiny compared with the 0.100 mol dm-3
coming from the sodium chloride solution.

In calculations like this, you can always assume that the

concentration of the common ion is entirely due to the other
solution. This makes the maths a lot easier. In fact if you don't
make this assumption, the maths of this can become impossible
to do at this level.

So we assume:

[Cl- ] = 0.100 mol dm-3

The rest of the sum looks like this:

Finally, compare that value with the simple saturated solution we

started with:
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Original solution:

[Pb2+] = 0.0162 mol dm-3

Solution in 0.100 mol dm-3 NaCl solution:

[Pb2+] = 0.0017 mol dm-3

The concentration of the lead(II) ions has fallen by a factor of

about 10.

If you tried the same sum with more concentrated solutions of

sodium chloride, the solubility would fall still further. Try it
yourself with chloride ion concentrations of 0.5 and 1.0 mol dm-
3.

Note: If you can be bothered to do this, don't just swap the

values in the last sum. Work it out for yourself from scratch -
it's good to practise!

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 the common ion effect

answers

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© Jim Clark 2011 (modified December 2013)

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