Solubility Product

The concentrations of ions in saturated solutions have a relationship to one another

somewhat like the relationship between the concentration of H3O+ and OH- in water.

Sodium Chloride

Consider saturated sodium chloride solution. Quite a bit of sodium chloride can be
dissolved in water, about 6 moles in one liter. That makes the concentration of both
the sodium ion and the chloride ion about 6 M. What happens if we increase the
concentration of Cl- by adding some concentrated hydrochloric acid (12M HCl)?. The
saturated NaCl is in the test tube and the concentrated HCl is in the dropper.
If nothing happened, we would still have
6M Na+ and a higher concentration, Approximate
-
perhaps, 8M, of Cl . But something does Concentrations
happen. Crystals of NaCl form from the [Na+] [Cl-]
-
reaction of some of the extra Cl with
Start 6M 6M
some of the Na+ that was in the solution.
The concentration of Na+ goes down to Potential 6M 8M
-
around 5 M as the conc of Cl increases to Actual 5M 7M
somewhere around 7M.

As the concentration of one ion increases, the concentration of the other ion
decreases. Just as there was an equation that related the concentrations of the
dissociated ions of water, there is an equation that relates the concentrations of the
dissociated ions of sodium chloride.

We can compare this equilibrium to the water ionization equilibrium.

Water ionizes to form H3O+ and OH-. 2 H2O H3O+ + OH-

The reaction is reversible. 2 H2O H3O+ + OH-

The concentrations of H3O+ and OH- are
Kw = [H3O+] [OH-]
related by this equation:
When multiplied together, the concentrations of H3O+ and OH- give a fairly constant
value called the ionization constant of water, or Kw.

Returning to sodium chloride we can see a similar relationship between the ions and
solid (excess) as we have with the H3O+ and OH- and the (excess) liquid water.

Sodium chloride dissolves and dissociates

NaCl(s) Na+ + Cl-
in water to Na+ and Cl-.
The reaction is reversible: NaCl(s) Na+ + Cl-
The concentrations of Na+ and Cl- are
Ksp = [Na+][Cl-]
realated by this equation:
When multiplied together, the concentrations of Na+ and Cl- give a fairly constant
value called the solubility product constant, or Ksp. For sodium chloride, the value of
Ksp is about 36.

Practice

See if you can figure out what the concentration of Na+ would be if we were able to
increase the concentration of Cl- up to 10 M. Take a moment to figure that out.

Answer

You should have calculated about 3.6 M

for the sodium ion concentration. I got
that value by saying that the Ksp = [Na+]x[Cl-]
concentration of Na+ times the [Na+] = Ksp ÷ [Cl-]
concentration of Cl- is equal to 36 (the Ksp
value for sodium chloride). If the [Na+] = 36 ÷ 10
concentration of Cl- is going to be 10 M, [Na+] = 3.6M
then the concentration of of Na+ has to be
36 divided by 10. That comes at to 3.6 M.

Silver Chloride

The same line of reasoning can be used with any salt that dissolves in water, even if it
dissolves only a very small amount.

Silver chloride will dissolve somewhat in

water. However, it reaches saturation very
quickly--that is, when the concentrations AgCl(s) Ag+ + Cl-
of silver and chloride ions are about 1.3 x
10-5M.
Still we can write a solubility product
Ksp = [Ag+][Cl-]
equation for it.
The value for the Ksp of silver chloride,
however, is about 1.8 x 10-10, a very small Ksp = 1.8 x 10-10
number.
Practice

Try using that information to calculate the Ag+ concentration if the chloride ion
concentration were 3.0 M.

Answer

Ksp = [Ag+]x[Cl-]
In this case the answer turns out to be a [Ag+] = Ksp ÷ [Cl-]
very small number, which can be
calculated using the process shown here. [Ag+] = (1.8 x 10-10) ÷ 3.0
[Ag+] = 6.0 x 10-11M

Lead(II) Chloride

When the formula for a salt contains more than just one of each ion, the solubility
product equation gets a little more complicated.

Let's use PbCl2 as an example. When PbCl2

cissolved in water, two ions of Cl- are PbCl2(s) Pb2+ + Cl-
released for every one ion of Pb2+.
When saturation is reached we show that
PbCl2(s) Pb2+ + 2 Cl-
the reaction is reversible.
The equation for the solubility product is: Ksp = [Pb2+][Cl-]2
The concentration of Cl- is squared because the balanced equation for the reaction
shows a 2 as the coefficient in front of Cl-.
PbCl2(s) Pb2+ + Cl- + Cl-
Looking at the reaction in this way might
then: Ksp = [Pb2+][Cl-][Cl-]
help you to remember that:
thus: Ksp = [Pb2+] [Cl-]2

Example - Determining concentrations at equilibrium

Here is an example of how to calculate the equilibrium concentration of one

substance given the Ksp and the equilibrium concentrations of the other substance.

For the reaction Ksp = [Pb+2] x [Cl]2

PbCl2(s) Pb+2(aq) + 2 Cl-(aq), 2.0 x 10-5 = [Pb+2] x (2.0 x 10-3)2
+2
what is [Pb ] at equilibrium 2.0 x 10-5 = [Pb+2] x 4.0 x 10-6
if [Cl-] = 2.0 x 10-3 M 2.0 x 10-5
given that the Ksp = 2.0 x 10-5? = [Pb+2]
4.0 x 10-6
5.0 M = [Pb+2]

Practice Problems: Equilibrium Concentrations

The Ksp for AgCl is 1.8 x 10-10. If Ag+ and Cl- are both in solution and in equilibrium
with AgCl. What is [Ag+] if [Cl-] = .020 M?

If Ag+ and Cl- were both present at 0.0001 M, would a precipitate occur?

What concentration of Ag+ would be necessary to bring the concentration of Cl- to

1.0 x 10-6 M or lower?

Answers: Equilibrium Concentrations

Here are the answers to the questions above.

The Ksp for AgCl is 1.8 x 10-10. If Ag+ and Cl- are both in solution and in equilibrium
with AgCl. What is [Ag+] if [Cl-] = .020 M?

[Ag+] = 9.0 x 10-9M

If Ag+ and Cl- were both present at 0.0001 M, would a precipitate occur?

Yes, a precipitate would occur because these concentrations together are higher than
what the Ksp allows.

What concentration of Ag+ would be necessary to bring the concentration of Cl- to

1.0 x 10-6 M or lower?

[Ag+] = 9.0 x 10-9M or higher