Solubility Product Ksp

Introduction
• Equilibria involving ions in aqueous solution are important in
– industrial, analytical and biological processes.

• The principles and characteristics of these ionic equilibria are very

similar to those in other systems in chemical equilibrium.

• The dissolving and precipitating of compounds are phenomena that

occur both within us and around us. E.g.;
– The dissolving of enamel in teeth in acidic solutions causes tooth decay;
– The precipitation of certain salts in our kidneys produce kidney stones;
– the precipitation of calcium carbonate from underground water to form
stalactites and stalagmites inside caves.
 SOLUBILITY AND SATURATED SOLUTIONS
The following table shows the solubility of some common ionic salts that you
should have come across. It provides a good starting point to discuss the
concept of solubility.
 SOLUBILITY AND SATURATED SOLUTIONS
• The units for solubility are usually in g dm –3 or mol dm –3 (molar
solubility)
• The solubility of a compound is defined for a given temperature. It
changes with changing temperatures.

• A supersaturated solution is a solution that contains a greater

amount of solute than that needed to form a saturated solution.
– They can be prepared by saturating a solution at high temperature followed
by slow cooling to a temperature at which the solute is less soluble.
– Addition of a small crystal of the solute to the supersaturated solution will
often lead to crystallization of the salt.
 IONIC PRODUCT
• For any ionic compound, as more solute is dissolved in a solvent, the
concentration of the solute particles (ions) in the solution increases, but this
cannot occur indefinitely.

• For most solutes, they have a limited solubility in a particular solvent. At a given
temperature, when this upper limit is reached, the solution is said to be
saturated.

• Additional solute will not dissolve when added to such a solution.

• A dynamic equilibrium is set up between the dissolved solute and the

undissolved solute.

• Thus, there is a constant dissolution of the excess undissolved solute and a

constant precipitation of the solid solute from the ions formed by the already
dissolved solute; these two processes take place at the same rate.
 IONIC PRODUCT
• Sparingly soluble ionic compounds (e.g. silver chloride, barium
sulfate, and iron(III)hydroxide) have low solubilities, so they reach
equilibrium with relatively little solute dissolved.
– Given that AgCl is a sparingly soluble salt, dissolution of AgCl is a reversible
process
• The ionic product of AgCl is therefore given by:

– It simply tells us how much ions are currently in the solution just upon
mixing, regardless of whether the solution is saturated or otherwise.
 SOLUBILITY PRODUCT
• At equilibrium, it is a mixture of the dissolved ions at saturation
with some of the undissolved solid.

• However, [AgCl] represents the ‘concentration’ of a pure solid, and is

therefore a constant. Thus,
 SOLUBILITY PRODUCT

• The new equilibrium constant, Ksp, is called the solubility product of

AgCl.

• In other words, the solubility product is the ionic product of

a sparingly soluble salt when the system is at equilibrium
 Ksp, the solubility-product constant.
An equilibrium can exist between a partially soluble
substance and its solution:
 What is solubility product?
https://www.youtube.com/watch?v=WjiXbemBXkE

• It is an equilibrium that exist when a chemical compound in

the solid state is in chemical equilibrium with a solution of that
compound.
– It explores the relationship between the solubility product of an ionic
compound and its solubility.
OR
 Example
• Note the BaSO4 (s) does not
appear in the expression.
The equilibrium constant is called the
solubility product, and is given the
symbol Ksp. • In a heterogeneous equilibrium,
concentration terms for solids
are not included because they
The unit for solubility product above are constant
(mol dm-3) x (mol dm-3)
= mol2 dm-6
Note:
• In the case where multiple ions are dissociated
Na3PO4 (s) ⇌ 3Na+ (aq) + PO43- (aq)
Ksp = [Na+]3[PO43-]

Unit of Ksp
• Like other equilibrium constants the unit of Ksp will vary
depending on the expression.
Ksp = [Na+]3[PO43-] = [mol dm-3]3 [mol dm-3]
= mol4dm-12
 USING IP AND Ksp TO PREDICT THE OCCURRENCE OF PRECIPITATION

• By comparing the value of the ionic product against the solubility

product of a salt, it is possible to predict the occurrence
of precipitation.

• Precipitation is said to occur when two solutions upon mixing

produce an insoluble solid (called the precipitate).
USING IP AND Ksp TO PREDICT THE OCCURRENCE OF PRECIPITATION

• If the ionic product (Qsp) < Ksp then no precipitate is formed

• If the ionic product (Qsp) = Ksp then a saturated solution is formed

• If the ionic product (Qsp) > Ksp then a precipitate is formed

https://www.youtube.com/watch?v=TBtaeyKkykU
 Question

Qsp=[Ca2+] [SO42-]
Qsp =Ksp for precipitation to occur

[Ca2+] [SO42-] = 2.40x 10-5

[Ca2+] = 2.40x 10-5 = 2.40x 10-5 mol2 dm-6 = 1.2 x10-1 mol/dm3
[SO42-] 2.00x 10-4 mol/dm3
 Try
• Will a precipitate form when an aqueous solution containing 6.00 x 10-5
mol/dm3 barium chloride is added to an equal volume of 1.20 x 10-5
mol/dm3 sodium sulphate? Ksp of Barium Sulphate is 2.45 x 10-5
Solution tips
• Calculate conc. of each reactant in the vol. given

you can use:

C1V1 = C2V2 (note: V2 is the total volume)
• State the dissolution rxn

• State the expression for Q

• Compare the values of Q and K and state whether a ppt will be

sp
formed
 SELECTIVE PRECIPITATION OF IONS
• Ions can be separated from each other based on the different
solubilities of their salts

• Selective precipitation: separation of ions in an aqueous solution

by using a reagent that forms a precipitate with one or a few of
the other ions but not all.

• Example of selective precipitation in nature:

– The precipitation of certain salts in our kidneys produce kidney stones.
 Precipitation in Nature: Kidney Stones
• Produced by the precipitation of substances naturally present in the
urine. The deposition (removal) depends on many factors.
– If the urine is too concentrated, the solubility product of some ions may be
exceeded and precipitates such as calcium phosphate and calcium oxalate
may build up.
– A higher concentration of calcium ions than normal may also shift the
equilibrium in favour of the precipitation of insoluble calcium salts such as
calcium carbonate and calcium phosphate, especially if conditions become
too alkaline.
https://www.youtube.com/watch?v=W0GpIMNTPYg&t=162s
– You can read up extra on this
 SELECTIVE PRECIPITATION OF IONS
Question
A solution contains 1.6 x 10-4 M Mg (NO3)2 and 2.0 x 10-6 M Ca(NO3)2. If F-
is added to the solution, will MgF2 or CaF2 precipitate first? (The Ksp values
for MgF2 and CaF2 are 6.0 x 10-9 and 4.0 x 10-11)

Solution tips
1.Find the conc. of F- that is needed to precipitate each substance
2.Write the dissolution rxn for each substance
3.Write the Ksp expression for the respective reactants / substance
4.Solve to find the unknown in each case
Note that the lower of the two concentrations for the common ion found will indicate that
that substance will precipitate first
Recall that Ksp indicated the max. conc of ions of the salt in the soln
 Solution
Question
A solution contains 1.6 x 10-4 M Mg (NO3)2 and 2.0 x 10-6 M Ca(NO3)2. If F-
is added to the solution, will MgF2 or CaF2 precipitate first? (The Ksp
values for MgF2 and CaF2 are 6.0 x 10-9 and 4.0 x 10-11)
1. MgF2 ⇔ Mg2+ + 2F- CaF2 ⇔ Ca2+ + 2F-
Q= [Mg2+] [F-]2 Q= [Ca2+] [F-]2
Q=Ksp for precipitation to occur Q=Ksp for precipitation to occur

[Mg2+] [F-]2 =6.0 x10-9 [Ca2+] [F-]2 =4.0 x10-11

[F-]2=6.0x10-9/ [Mg2+]
= 6.0 x 10-9/1.6x10-4 = 3.75x10-5
[F-]=(3.75x10-5)½ = 6.32x10-3
This value of [F-] tells you that this is the minimum amount
of F- that will cause MgF2 to precipitate out. It is higher and
therefore MgF2 will precipitate last
[F-]2=4.0 x10-11/ [Ca2+]
= 4.0 x10-11/2.0x10-6 = 2.0 x 10-5
[F-]=(2.0 x 10-5)½ = 4.47x10-3
This value of [F-] tells you that this is the minimum amount
of F- that will cause CaF2 to precipitate out. It is lower and
therefore CaF2 will precipitate first
 Try

b) Which salt precipitates first and why?

 Precipitation and Qualitative Analysis
• We can use solubility data to choose suitable reagents to selectively
precipitate compounds from their solutions.
– For example, we use silver nitrate to test for halide ions such as Cl-, Br- and
I-

• Most halides are soluble in water as are most nitrates. But silver
halides have very low solubility product. So adding only a few drops
of silver nitrate to a halide ion results in a precipitate e.g.
Ag+ (aq) + Cl- (aq) => AgCl (s)
– These precipitates (ppt) can be distinguished by their characteristic colours.
review grade 11 qualitative info:
 Determining Solubility Product by Experiment
• The method is based on making a saturated solution of a particular
substance and analyzing the solution to find the concentration of a
particular ion which is present in the solid as well. For example to find
Ksp for calcium hydroxide, Ca(OH)2:
– Add enough calcium hydroxide to a known volume of water so that solid is
present as well as solution. Shake and leave for 24 hours to reach
equilibrium
– Filter off the solid calcium hydroxide.
– Titrate the samples of the calcium hydroxide solution with hydrochloric acid
of known concentration.
– Calculate the concentration of the calcium hydroxide solution from the
titration results
– Find K by substituting in the equilibrium expression
 Limitations of Ksp
• Ksp is valid only for saturated solutions in which the concentrations
of the ions is no more than 0.01 mol/dm3 (i.e. for solutions of
substances that are sparingly soluble)

• Ksp is affected by temperature since it is an equilibrium constant

 Think about it…
• How can Ag+ be separated from Pb2+ ? Is the separation effective
• Note the difference in solubilities
 Calculating solubility products from solubilities
• Assume that you are given the solubility of an ionic compound in mol dm- 3. If it was in g dm-3, or any other
concentration units, you would first have to convert it into mol dm -3.

Example 1
The solubility of barium sulphate at 298 K is 1.05 x 10-5 mol dm-3. Calculate
the solubility product.

The equilibrium is:

• Notice that each mole of barium sulphate dissolves to give 1 mole of

barium ions and 1 mole of sulphate ions in solution.
 That means that:
• [Ba2+] = 1.05 x 10-5 mol dm-3
• [SO42-] = 1.05 x 10-5 mol dm-3
Put these values into the solubility product expression, and solve
 Example 2
• The solubility of magnesium hydroxide at 298K is 1.71 x 10-4
mol dm-3. Calculate the solubility product.
Mg(OH)2 ⇔ Mg2+ + 2OH-
Example 3
Example 4
 YOU TRY
• A saturated solution of PbCl2 has the concentration of [PbCl2 (aq)] of
3.5 x 10–2 mol dm–3
– Calculate the Ksp for this solution

– Question
 Calculating solubilities from solubility
products
• If the solubility product of magnesium hydroxide is 2.00 x 10-11 mol3 dm-9 at
298 K, calculate its solubility in mol dm-3 at that temperature.

• If the concentration of dissolved magnesium hydroxide is s mol dm-3, then:

[Mg2+] = s mol dm-3
[OH-] = 2s mol dm-3
Solution
 Question:
• A solution is prepared by mixing 200ml of 0.10M Ca(NO3)2 soln with
300ml of 0.25M NaF soln.

a)Calculate the equilibrium concentration of Ca 2+ and F- in the soln.

the Ksp value for the CaF2 is 4 x 10-11
Will precipitation occur in this solution?
Qsp= [Ca2+][F-]2 Conc. of Ca2+: Conc. of F-:
Qsp= 0.04 x 0.152 C1V1 = C2V2 using same
Qsp=9x10-4 C2=C1V1/ method= 0.15M
Qsp> Ksp C2=(0.1x0.2)/0.5
Hence, ppt will occur =0.04M
 Question
• Calculate the solubility in in mol dm-3 of calcium sulphate , CaSO4 if
Ksp is 2.00 x 10-5 mol2 dm-6 .
CaSO4 ⇔ Ca2+ + SO42-
Solution
• Ksp = [Ca2+][SO4-] making concentration = x then
Ksp = [x][x] or [x]2
[x]2 =2.00 x 10-5 mol2 dm-6
X= √ 2.00 x 10-5 mol2 dm-6
= 4.47 x10-3 moldm-3
Question
Question:
The Ksp for silver phosphate, Ag3PO4, is 1.25×10–20 .
– Calculate [Ag+(aq)] in a saturated solution of Ag3PO4.

• Ksp = [Ag+]3 [PO43-]

• make [PO43–] = y and therefore [Ag+ ] = 3y
Ksp = [3y]3 [y] = 27y4
y = (Ksp / 27) ¼
y = (1.25 × 10–20 / 27) ¼ = 4.64 × 10–6 mol dm–3
[Ag+ ] = 3y
= 1.39 × 10–5 mol dm–3
 You Try

– Question
 Common ion effect
• The common ion effect is responsible for the reduction in
solubility of an ionic precipitate when a soluble compound
containing one of the ions of the precipitate is added to the
solution in equilibrium with the precipitate.

What happens if you add some sodium chloride to this saturated solution?
 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.
 Common ion effect
• 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.
 Common ion effect
• The solubility of Ca(OH)2 in 0.1 mol dm–3 NaOH is lower than
that in water.

• Ca(OH)2 (s) ⇌ Ca2+ (aq) +2 OH- (aq)

• Ca(OH)2 is less soluble in NaOH due to the common hydroxide

ion effect. It causes the equilibrium to be shifted to the left
because of the higher hydroxide ion concentration
 Common ion effect

1. A solution is made by mixing 500.0 mL of 0.12 M NaOH solution with

500.0 mL of 0.10 M Mg(NO3)2.
• Ksp is 1.8 × 10-11

• (a) Assuming that no reaction occurs, what will [Mg2+(aq)] and [OH-(aq)]
be after mixing?
– Recall finding conc using C1V1 = C2V2; where V2 is the total volume

• (b) Write down the value of the ionic product, Qsp.

• (c) Does a precipitate form?

 Soln
(a) [Mg2+(aq)] = 0.050 M and [OH-(aq)] = 0.060 M

(b) Qsp = [Mg2+(aq)] [OH-(aq)]2 = (0.050)(0.060)2 = 1.8 × 10-4

(c) Qsp > Ksp so Mg(OH)2 (s) precipitate forms

 Common ion effect

• For each of the following experiments, predict whether or not a

precipitate of MgF2 will form.

• Ksp MgF2(s) = 6.4 × 10-9

• (a) 500.0 mL of 0.050 M Mg(NO3)2 is mixed with 500.0 mL of 0.010 M NaF

• (b) 500.0 mL of 0.050 M Mg(NO3)2 is mixed with 500.0 mL of 0.0010 M

NaF.
 Soln
( a) After mixing, [Mg2+(aq)] = 0.025 M and [F-(aq)] = 0.0050 M.

Qsp = [Mg2+(aq)][F-(aq)]2 = (0.025)(0.0050)2 = 6.3 × 10-7

Qsp > Ksp so precipitation will occur.

(b) After mixing, [Mg2+(aq)] = 0.025 M and [F-(aq)] = 0.00050 M.

Qsp = [Mg2+(aq)][F-(aq)]2 = (0.025)(0.00050)2 = 6.3 × 10-9

Qsp < Ksp so no precipitation will occur.

 Common ion effect

Ksp = [Ag+] [Cl-]

2 x 10-10 = s2 (note: let ‘s’ be the conc of Ag+ and Cl- @
equil)
(2 x 10-10 )½ = s2
1.41 x 10-5 =s
https://www.youtube.com/watch?v=qawipem0LwA&t=156s
Ksp= [Ag+] [Cl-]

AgCl → Ag+ + Cl-

Initial 0 0.1 → (From NaCl)
Change +x +x
Equilibrium +x 0.1+x(assume that this is equal to 0.1)

Ksp= [Ag+] [Cl-]

2.00x 10-10= x(0.1) therefore x= 2.00x 10-10/0.1 = 2.00x 10-9M
 Past paper question
Gypsum (CaSO4.2H2O) is a common mineral found worldwide. It
is slightly soluble in water, and ground water that is is in contact
with gypsum contains some calcium sulphate (CaSO4).
a) Write the equation which represent the equilibrium between

Ca2+(aq) and SO42-(aq) and undissolved CaSO4

__________________________________________(1 mark)

a) Explain the meaning of the term solubility product

_________________________________________ (1 mark)
• State one physical factor which affects the value of the solubility
product constant [1]

• In bronzing an ornamental work requiring a golden colour, lead

iodide PbI2 which can be described as a dense, golden yellow
insoluble solid, is used.

• Calculate the solubility of PbI2 in water@ 25 C using the solubility

product constant (Ksp) = 7.1 x 10-9 mol3dm-9 [5]

How is the solubility of a slightly soluble ionic compound affected when

a second solute that furnishes common ion is added