Chemistry 12 Unit 3 - Solubility of Ionic Substances
Tutorial 7 - The Common Ion Effect and Altering Solubility Page 1
In Tutorial 7, you will be shown:
1. What the Common Ion Effect is and how it can be used.
2. How we can increase or decrease the solubility of a compound by adding other materials.
The Common Ion Effect
To understand the Common Ion Effect, you must first review LeChateliers Principle.
Remember, it goes something like this:
Le Chateliers Principle:
When a stress is applied to a system at equilibrium, the equilibrium will shift so as
to partially counteract the imposed stress.
Lets see how this might apply to solubility.
We can start by looking at the equilibrium equation for a compound of low solubility, eg.
CaCO
3(s)
:
CaCO
3(s)
Ca
2+
(aq)
+ CO
3
2-
(aq)
Lets say we have a saturated solution of calcium carbonate (CaCO
3
). What this means is that we
would have some solid CaCO
3
sitting on the bottom of the solution and there would be some Ca
2+
ions and some CO
3
2-
ions dissolved in the solution.
CO
3
2-
Ca
2+
A saturated solution of
CaCO
3
CaCO
3 (s)
Chemistry 12 Unit 3 - Solubility of Ionic Substances
Tutorial 7 - The Common Ion Effect and Altering Solubility Page 2
Since this solution is at equilibrium, the concentration of dissolved Ca
2+
and CO
3
2-
ions in
solution will stay constant. (Even though ions are dissolving and precipitating all the time--at rates
which just balance each other.) This situation would remain constant through eternity unless we
do something.
Lets say we add a small amount of Calcium Chloride (CaCl
2
) to the beaker. Calcium chloride is
considered soluble, so we can assume that it all dissociates into Ca
2+
and Cl
-
ions: (Notice the single
arrow!)
CaCl
2(s)
! Ca
2+
(aq)
+ 2Cl
-
(aq)
So what we would be doing is adding some Ca
2+
ions and some Cl
-
ions to the solution in the
beaker.
But remember, the solution in the beaker was already saturated with Ca
2+
and CO
3
2-
ions from the
CaCO
3
! So what in the world will happen now?
CO
3
2-
Ca
2+
CaCO
3 (s)
Cl
-
Ca
2+
Since there were no Cl
-
ions in the solid or in the solution before, they will not affect anything.
They can be regarded as spectator ions in this case.
But you can see by the diagram that we are adding Ca
2+
ions to a saturated solution of CaCO
3
.
Looking at the equilibrium equation for CaCO
3(s)
dissolving:
CaCO
3(s)
Ca
2+
(aq)
+ CO
3
2-
(aq)
What we are actually doing is increasing the [Ca
2+
] in this equilibrium. This, of course is
imposing a stress on the system at equilibrium.
By LeChateliers Principle, increasing the [Ca
2+
] can be counteracted by the equilibrium shifting
to the LEFT:
CaCO
3(s)
Ca
2+
(aq)
+ CO
3
2-
(aq)
What this will do is increase the amount of CaCO
3(s)
and decrease the concentration of CO
3
2-
.
CaCO
3(s)
Ca
2+
(aq)
+ CO
3
2-
(aq)
Chemistry 12 Unit 3 - Solubility of Ionic Substances
Tutorial 7 - The Common Ion Effect and Altering Solubility Page 3
Since this results in more solid CaCO
3
in the beaker, we can say that:
Adding Ca
2+
ions to the solution decreases the solubility of CaCO
3
.
Now, hopefully you can see where the name Common Ion Effect fits in.
The ion Ca
2+
that was added to the saturated CaCO
3
solution is the same as (common to) one of
the ions in the original solution.
We can now generalize a little bit:
A compound of low solubility forms two ions in a saturated solution. The addition of either of
these two ions (from a compound or solution with an ion in common) will decrease the solubility
of the compound with low solubility.
Using this concept, we can see that many compounds could decrease the solubility of CaCO
3
.
Increasing Solubility
We can use LeChateliers Principle for increasing the solubility of a compound as well as for
decreasing it (as we did with the Common Ion Effect).
Lets look at this equilibrium again:
CaCO
3(s)
Ca
2+
(aq)
+ CO
3
2-
(aq)
If we could somehow decrease either [Ca
2+
] or [CO
3
2-
], then this equilibrium would shift to the
right and the amount of solid would decrease. (ie. the solubility would increase.)
But, how do we decrease the concentration of an ion? We cant just reach in and pull ions out of a
solution! But, there IS a way.
The carbonate (CO
3
2-
) ion happens to be easy to decrease. All we have to do is add some acid
to the container. The following sequence of reactions will (hopefully) help you understand how
this works. Just remember, what we are trying to do is decrease the [CO
3
2-
] in this equilibrium:
CaCO
3(s)
Ca
2+
(aq)
+ CO
3
2-
(aq)
Chemistry 12 Unit 3 - Solubility of Ionic Substances
Tutorial 7 - The Common Ion Effect and Altering Solubility Page 4
Now, focus your attention just on the carbonate:
CO
3
2-
(aq)
As you might know, when you put an acid into water, hydrogen ions (H
+
) are formed.
(eg. HCl
(g)
! H
+
(aq)
+ Cl
-
(aq)
)
Well, when these hydrogen ions collide with carbonate, they temporarily form a compound called
carbonic acid. Lets see:
2H
+
(aq)
+ CO
3
2-
(aq)
! H
2
CO
3 (aq)
C
O
O
O
H
+
H
+
CO
3
2-
2 H
+
+
C
O
O
O
H
H
H CO
2
3
hydrogen ions carbonate ion carbonic acid
(from acid)
Now, it so happens that carbonic acid (H
2
CO
3
) is unstable in water solution. Carbonic acid is
actually what is present in carbonated beverages (like pop).
In water solution, carbonic acid (H
2
CO
3
) decomposes to form carbon dioxide gas (CO
2(g)
) and
liquid water :
H
2
CO
3 (aq)
! H
2
O
(l)
+ CO
2 (g)
C
O
O
O
H
H
H CO
2 3
This H
breaks off
here and
moves to
the other O
This bond
weakens and
breaks
O
H
H
C
O
O
+
H O + CO
2 2
decomposes
(l)
(g) (aq)
What happens now is the carbon dioxide gas escapes (in the form of bubbles) from the solution.
Because the CO
2
escapes, this reaction keeps proceeding to the right.
Chemistry 12 Unit 3 - Solubility of Ionic Substances
Tutorial 7 - The Common Ion Effect and Altering Solubility Page 5
In other words, as soon as some carbonic acid (H
2
CO
3
) is formed, it decomposes into CO
2(g)
and
water, and then the CO
2(g)
escapes into the air. Because the CO
2
escapes, the reverse reaction
does not have a chance to take place.
Now, recall the equilibrium:
CaCO
3(s)
Ca
2+
(aq)
+ CO
3
2-
(aq)
As was said there, something that would decrease the [CO
3
2-
] would shift this equilibrium to the
right and dissolve more solid CaCO
3
(increase its solubility).
Then we learned that by adding an acid (contributing H
+
ions), that the CO
3
2-
is used up to make
carbonic acid (H
2
CO
3(aq)
) which then decomposes to H
2
O and CO
2(g)
, which escapes into the air.
This can all be summarized by the following:
CaCO
3(s)
Ca
2+
(aq)
+ CO
3
2-
(aq)
H
+
(from acid)
H
2
CO
3(aq)
decomposes
!!!!!!!!!
H
2
O
(l)
+ CO
2(g)
So we have represented three reactions here. The ones going down the right side result in a
decrease in [CO
3
2-
] in the first equilibrium (which is the one to really focus on here.)
Since the [CO
3
2-
] is decreased, the equilibrium will shift to the right, increasing the solubility of
CaCO
3(s)
.
CaCO
3(s)
Ca
2+
(aq)
+ CO
3
2-
(aq)
As a result, more CaCO
3(s)
dissolves and the [Ca
2+
] and [CO
3
2-
] goes up (to compensate for the
decrease in [CO
3
2-
] caused by adding the acid.)
CaCO
3(s)
Ca
2+
(aq)
+ CO
3
2-
(aq)
As long as more acid is added, this process will continue until all the solid CaCO
3
has been
dissolved.
It is important to realize here that this reaction is specific to compounds with the carbonate ion.
Adding an acid may work with a few other ions like sulphite (SO
3
2-
), but not all of them ! In
Chem. 12, it is important to remember that:
Chemistry 12 Unit 3 - Solubility of Ionic Substances
Tutorial 7 - The Common Ion Effect and Altering Solubility Page 6
Adding an acid to a low solubility compound with carbonate, will decrease the
[CO
3
2-
] and increase the solubility of the compound.
Increasing Solubility by Forming Another Precipitate
Remember, if we decrease the concentration of an ion in a solubility equilibrium, the equilibrium
will shift right and increase the solubility of the solid:
For example, if in the following equilibrium, [Ag
+
] is decreased, the equilibrium will shift right
and some of the solid AgCl will dissolve:
AgCl
(s)
Ag
+
(aq)
+ Cl
-
(aq)
Well, now we will show you another way to decrease the concentration of a specific ion (like
Ag
+
).
What you can do is add something that will form a precipitate with Ag
+
. This will decrease the
[Ag
+
] in the solution.
So what you are really doing is forming one precipitate to dissolve another one.
Firstly, it would be a mistake to add chloride ions (Cl
-
), as this would just make this equilibrium
shift left and decrease the solubility of AgCl. We are trying to do the opposite!
It is found that if you add sulphide (S
2-
) ions to this solution, that the S
2-
will form a precipitate
with the silver (Ag
+
) ions. This process can be represented by the following:
AgCl
(s)
Ag
+
(aq)
+ Cl
-
(aq)
+
S
2-
(S
2-
is added)
Ag
2
S
(s)
So basically, the Ag
+
ions are being pulled from the AgCl equilibrium to form the precipitate
Ag
2
S
(s)
.
Of course, you cant just add sulphide (S
2-
) ions by themselves. You would have to add a solution
containing a soluble compound of sulphide. A soluble compound of sulphide is sodium sulphide
(Na
2
S
(aq)
).
You could consult your Solubility Table to find an ion (other than Ag
+)
that would form a
precipitate with Cl
-
. Our table says that Pb
2+
ions precipitate Cl
-
ions.
Chemistry 12 Unit 3 - Solubility of Ionic Substances
Tutorial 7 - The Common Ion Effect and Altering Solubility Page 7
So you could add a solution of a compound containing Pb
2+
(eg. Pb(NO
3
)
2(aq)
) to the container
with the AgCl.
AgCl
(s)
Ag
+
(aq)
+ Cl
-
(aq)
+
Pb
2+
(Pb
2+
is added)
PbCl
2(s)
Now the Pb
2+
ions react with the Cl
-
ions from the AgCl equilibrium, forming a new precipitate
(PbCl
2(s)
) and decreasing the [Cl
-
] in the solution. Doing this causes the AgCl equilibrium to shift
to the right, thus dissolving the AgCl
(s)
.
You can always use your solubility table to find a compound that will precipitate a certain ion from
solution. Remember, the table gives you just ions.
For any positive ion that is needed, putting the negative ion nitrate (NO
3
-
) with it is always a safe
bet as NO
3
-
will not form any unwanted precipitates and compound with NO
3
-
are all soluble, so
they will be readily break up to supply the ions you want.
For any negative ion that you need, it is safe to use the sodium (Na
+
) or potassium (K
+
) salt of the
ion, since these would always be soluble and Na
+
or K
+
will not form any unwanted precipitates.
To quickly summarize what we have shown on Tutorial 7:
1. The solubility of a compound is decreased when an ion which is the same as one of the ions in the
compound (common ion) is present or added.
2. The solubility of compounds containing the carbonate (CO
3
2-
) ion can be increased by adding an
acid. The H
+
ions from the acid react with the carbonate (CO
3
2-
) forming carbonic acid
H
2
CO
3(aq)
) which decomposes into water and CO
2(g)
. In this way the [CO
3
2-
] is decreased in the
solubility equilibrium for the original compound, the equilibrium shifts toward the side with the
ions, and the solid dissolves more.
3. The solubility of a compound can be increased by adding a solution that will form a precipitate
with one of the ions in the compound. This will decrease the concentration of that ion, causing the
equilibrium to shift to the ion side and dissolve the solid.