Solubility Equilibrium

Good News is
We are pretty good at solving general equilibrium problems.

Bad News is
There are many other types of equilibrium that AP folks are fond of.
Acid-Base Equilibrium (well save that for after Christmas) Solubility Equilibrium

Solubility Equilibrium
Involves reactions that occur in aqueous solutions and includes the formation and dissolving of precipitates
Utilizes our knowledge of solubility rules
Theyre back to haunt us!

Requires the ability to use stoichiometry

Remember your best friend, the mole map?

I Confess
That weve lied to you. When we told you that salts like silver chloride and copper (II) hydroxide were insoluble, we fudged a wee bit. Now might be a good time to review you solubility rules on page 179.

What We Meant to Say is That

If we place a tiny amount of silver chloride or some other insoluble salt into water, a very small amount does, in fact, dissolve. Once the solution becomes saturated (meaning it cant dissolve any more solute), equilibrium is established between the undissolved salt and its ions in solution.

Solubility Equilibrium
We can write an equilibrium expression, but instead of calling it a Kc or Kp, we call it a Ksp. Ksp. is called the solubility product constant because the system is a solubility equilibrium and the constant (not Michael) equals a product of ion concentrations. Because solubility is temperature-dependent, Ksp applies only at a specific temperature.

Writing Ksp Expressions

Its just like writing any other K expression, but with one minor difference. Because were talking about IONS, its not just coefficients that matter, but also subscripts. That means in order to write the Ksp, we must know the formula of the salt as well as the ions that comprise it.

Example 1
Write the expression for the equilibrium involved in the solubility of silver chloride corresponding to Ksp. AgCl (s) Ag+ (aq) + Cl- (aq) Ksp = [Ag+] [Cl-]

Example 2
Write the expression for the equilibrium involved in the solubility of aluminum hydroxide corresponding to Ksp. Al(OH)3 (s) Al3+ (aq) + 3OH- (aq) Ksp = [Al3+] [OH-]3

Example 3
Write the expression for the equilibrium involved in the solubility of barium phosphate corresponding to Ksp. Ba3(PO4)2 (s) 3Ba2+ (aq) + 2PO43- (aq) Ksp = [Ba2+]3 [PO43-]2

Homework
Page 896 #37, 38

So far
Weve used a RICE table to calculate Ksp values and determine molar solubilities of salt equilibrium reactions. To this point, our solvent has always been water. What does this mean?
We were able to assume that the initial concentration of any ion in solution was zero.

What if
Our solvent isnt water, but contains some concentration of the same ion as is present in the salt? Clearly, our initial concentration of

THAT

ION would not be zero.

We can use this hypothetical situation (which is a practical application of solubility equilibrium) to explore whats called the common ion effect.

The Common Ion Effect

The solubility of one salt is reduced by the presence of another having a common ion.

 According to LeChateliers Principle, adding more product causes equilibrium to shift to the left, making more reactants. In this case, it makes more lead (II) chromate. This is evident by formation of a precipitate.

Solving Problems Involving Common Ion Effect

Use the 5 Easy Steps handout, but look for the presence of a common ion which would effect the initial concentration of ONLY that particular ion. Assume that the amount of common ion added to the solution is large compared to the amount of ion coming from the insoluble salt, so the change row of your common ion is negligible. Simplify your calculations using this assumption! Consult Appendix J in your textbook for values of Ksp.

Example 1
What is the molar solubility of PbI2 in a 0.10 M NaI solution?

Example 2
Calculate the molar solubility of AgI in a 0.20 M CaI2 solution.

Example 3
Calculate the molar solubility of Fe(OH)3 in a solution where the [OH-] is initially 0.050 M. Assume the dissociation of Fe(OH)3 is 100%.

Back to Q
Recall that Q is calculated much the same way we calculate K. For solubility equilibria, we calculate Q the same way we calculate Ksp. Remember that we never include pure solids or liquids in our equilibrium expression or in our Q calculation.

Will a precipitate form?

If Q > Ksp, the solution is supersaturated No more ions may be dissolved in the solution A precipitate will form If Q = Ksp, the solution is saturated The solution is holding all the ions it can A precipitate will not form UNLESS WE ADD MORE STUFF (LIKE IONS IN THE FORM OF SALT) If Q < Ksp, the solution is unsaturated More ions can be dissolved in the solution A precipitate will not form

Example 1
Suppose we want to prepare 0.500 L of a solution containing 0.0075 mol of NaCl and 0.075 mol of Pb(NO3)2. Will PbCl2 precipitate?

Example 2
Will a precipitate of CaSO4 form if we mix 0.0025 M CaCl2 and 0.030 M NaSO4?

Example 3
Will a precipitate form if we mix 3.4 x 10-4 M CrO4 2- and 4.8 x 10-5 M Ag+?