SOLUBILITY EQUILIBRIUM • is equal to the product of the
concentration of the ions in the
Solubility Product Constant Ksp
• is base on the assumption that solids
dissolve in water to give the basic
particles from which they are formed.
• Molecular solids dissolve to give
individual aqueous molecules.
• Ionic solids dissociate to give their
respective positive and negative ions:
• The ions in formed from the
dissociation of ionic solids can carry an
electrical current. Salt solutions,
therefore, are good conductors of
electricity.
• Molecular solids, however, do not
dissociate in water to give ions, so no
electrical current can be carried.
• is the equilibrium constant between an
ionic solute and its ions in a saturated
solution.
• A very small Ksp indicates that only a
small amount of solid will dissolve in
water.
equilibrium, each raised to the power of
its coefficient in the equation.
Degrees of Solubility
Solubility Product Constant Ksp
• A salt is considered soluble if it dissolves
in water to give a solution with a
concentration of at least 0.1 M at room
temperature.
• A salt is considered insoluble if the
concentration of an aqueous solution is
less than 0.0001 M at room
temperature.
• Salts with solubilities between 0.0001
M and 0.1 M are considered to be
slightly soluble.
• Salts that have extremely low
solubilities dissociate in water according
to the principles of equilibrium.
Example, the reaction for the dissociation of the
salt AgCl is:
• The reverse reaction for the dissolving
of the salt would be the precipitation of
the ions to form a solid:
 • The system has reached equilibrium Calculating solubility from Ksp
when the rate at which AgCl dissolves is
equal to the rate at which AgCl
precipitates. Calculate the solubility of Ca𝐹 2 in g/L

• NOTE: There is no denominator in the • First, write the BALANCED REACTION:

solubility product equilibrium constant.
• The key word to remember is PRODUCT
which can remind you that you should
have a multiplication (or product) of the
• Next, set up the SOLUBILITY PRODUCT
concentrations of the ions.
EQUILIBRIUM EXPRESSION:
• The reason that the solid reactant is not
written is because its concentration
effectively remains constant.

For example, the solubility product equilibrium

constant for the dissociation of AgCl is:

Solubility Product Constant Ksp

• If we SUBSTITUTE these values into the

equilibrium expression, we now only
have one variable to worry about, X:

• We can now SOLVE for X:

Solubility and Ksp

• Ksp can be calculated from the

solubility of a salt.
• Conversely, the solubility of a salt can
be calculated from Ksp.
 • [Ag+] is equal to [Cl-] at equilibrium
because the mole ratio of Ag+ to Cl- is
1:1.
• What would happen to the solution if a
tiny bit of AgNO3 (a soluble salt) were
added? Since AgNO3 is soluble, it
dissociates completely to give Ag+ and
NO3- ions. There would now be two
sources of the Ag+ ion, from the AgCl
and from the AgNO3:

• Adding AgNO3 increases the Ag+

concentration and the solution is no
longer at equilibrium.
• The ion product (Qsp) at that moment is
bigger than the solubility product (Ksp).
• The reaction will eventually return to
equilibrium but when it does, the [Ag+]
is no longer equal to the [Cl-]. Instead,
the [Ag+] will be larger than the [Cl-].
• Let's go back to the saturated AgCl
solution.
• What would happen this time if a tiny
bit of NaCl (a soluble salt) were added?
Ion Product (Qsp) Since NaCl is soluble, it dissociates
completely to give Na+ and Cl- ions.
• The product of the concentrations of
There would now be two sources of the
the ions at any moment in time (not
Cl- ion, from AgCl and from NaCl:
necessarily at equilibrium).
• Imagine we have a saturated solution of
AgCl. The equilibrium reaction for the
dissociation of this salt is:

• Adding NaCl increases the Cl-

concentration and the solution is no
longer at equilibrium. The ion product
(Qsp) at that moment is bigger than the
solubility product (Ksp). The reaction
will eventually return to equilibrium but
when it does, the [Ag+] is no longer
 equal to the [Cl-]. Instead, the [Cl-] will
be larger than the [Ag+].
The ion product (Qsp) can be used to determine
in which direction a system must shift in order
to reach equilibrium. There are three possible
situations:
Qsp < Ksp - This means there are not
enough ions in the solution. In order to return
to equilibrium, more of the solid salt must
dissociate into its ions.
Qsp = Ksp - This means that the system
is at equilibrium.
Selective precipitation
• Fractional precipitation
• A technique in which one ion is
selectively removed from a mixture of
ions by precipitation.
• Ions in a solution can be separated from
each other on the basis of the different
solubilities of their salts.
• Add HCl to a solution containing Ag+
and Cu2+ and only the AgCl precipitates
out.

Qsp > Ksp - This means that there are

too many ions in the solution. In order to return
to equilibrium, the excess ions will precipitate
to form more solid.

Common-Ion effect

• The decrease in the solubility of a salt

that occurs when the salt is dissolved in
a solution that already contains another
source of one of its ions.
• For example, if AgCl is added to a NaCl
solution (which contains the common
ion, Cl-) the solubility of the AgCl
decreases.