UNIT 11: SOLUBILITY AND SOLUBILITY

PRODUCT OF SPARINGLY SOLUBLE SALTS

This unit introduces us to solubility equilibria which is found in
saturated solutions of slightly soluble ionic salts

Specific examples of soluble salts include:

 All Nitrates,
 All Carbonates except calcium carbonate and silver
carbonate
 All Chlorides except Lead Chloride,lead
chlorides,mercury chlorides.
 Gp1 metal, and Ammonium Sulphate are also soluble,
Figure below summarizes the solubility of the
common salt in water at room temperature.
11.1. Unsaturated, saturated and super
saturated solutions
 A saturated solution is one which contains the
maximum amount of dissolved solid at a particular
temperature .
Adding one crystal of solute to a saturated solution, the
precipitation will be observed
 If the quantity of a substance in a solution is less than
that required to get the equilibrium with the solid, the
solution is said to be “unsaturated”.
If more solid is added to an unsaturated solution, it
dissolves until the solution is saturated at the point that
there is solid in equilibrium with the solvated ions.
 A super saturated solution contains more solute than a
saturated solution.
 11.2. Definitionof solubility and molar solubility
 The solubility is a chemical property referring to the
ability for a given substance( the solute) to dissolve in a
solvent.
 Solubility of a substance in a solvent is the concentration
of the saturated solution.

It is expressed in g.dm-3 or mol.dm-3,

 Molar solubility
Molar solubility can be expressed as the number of moles of
a solute that can be dissolved per liter of solution to get a
saturated solution.
NOTE: Solubility of ionic salts increases with increased
temperature.
Consider the following equilibrium:

AxBy + H2O y+ x-
xA + yB
[A y+ ] [ B x ]
s(A x By )= 
x y
[ A y  ]  x  s( Ax By )
[ B x ]  y  s( Ax By )

Example:
Calculate the molar solubility of sulphate
ions and barium ions in a saturated
solution of barium sulphate solution with
0.25mol.dm-3.
Answer:
Data: S (BaSO4)=0.25mol.dm-3
The dissociation equation is:

BaSO4(s) Ba2+(aq) + SO42-(aq)

S(BaSO4)=[Ba2+]=[SO42-]=0.25M
11.3. Definition of solubility product ksp
Solubility product of a salt (Ksp), is the product of the
concentrations of the ions in a saturated solution, raised to
the appropriate powers.
Consider the following equilibrium of a salt AxBy:

AxBy + H2O xAy+ + yBx-

The equilibrium constant for this equilibrium is called solubility product and
is given by:

Ksp  [ A y  ]x [ B x ] y

Note:
1) The units of Ksp depend on the units of concentration of ions in
its expression.
2) Ksp of a salt depends only on the temperature, if the temperature
changes, Ksp changes also.
Examples of expression of Ksp for some compounds

1. AgCl(s)↔Ag+(aq) +Cl-(aq)
Ksp of AgCl = [Ag+] [Cl-]

2. PbSO4(s) ↔ Pb2+(aq)+ SO42- (aq)

Ksp = [ Pb2+][ SO42-]

3. PbI2(s) ↔ Pb2+(aq)+ 2I-(aq)

Ksp = [Pb2+] [2I-]2

Note: Solubility products are only constant at a

particular temperature which is usually 298K.
Example: A saturated solution of silver chloride contains contains 1.46×10-3g/L at 18oC.
What is the solubility product of AgCl at this temperature?
Answer:
1.46 103
S ( AgCl ) 
143.5 g / mol 1L
 1.017 105 M
S ( AgCl )  [ Ag  ]  [Cl  ]
[ Ag  ]  1.017 105 M
[Cl  ]  1.017 105 M
Ksp  [ Ag  ][Cl  ]
 (1.017 105 M )(1.017 105 M )
 1.034 103 M 2
11.4. Relationship between solubility(s) and
solubility product (Ksp)

Consider the following reaction:

AmBn (s) mBn+ (aq) + nBm-(aq)

The expression of solubility of product constant is given by

Ksp = [An+]m[Bm-]n=(mS)mx(nS)n
m n m+n
= m xn xS
Example
1. The solubility of Ag2SO4 is 1.4. 10-2 mol / l.
Calculate its solubility product
2. The solubility product of strontium fluoride (SrF2) is
equal to 2.5. 10-9 at 25°C. What is the solubility of SrF2 in
water?
3. The solubility product of calcium phosphate,
Ca3(PO4)2 is 1.0×10-26M5.
at 250C. Calculate the solubility at this
temperature. (O =16, P =31,Ca=40)
Answer:

K sp  m  n  S
m n mn
 2 1  1.4 10
2 1

2 3
 1.09 105

Answer:
9
Ksp 3 2,5 10 4 mol
S m n   8.55  10
mm  nn 11  22 l

Answer: 7.7× 10-4g/dm3

Exercises
1. The solubility of calcium carbonate CaCO3, at 298K is 6.9×10-3
moldm-3. Calculate the solubility product at this temperature.
Answer: 4.8×10-6 mol2dm-6
2. The solubility of calcium sulphate CaSO4 at 298K is 0.67g/dm3.
Calculate the solubility product at this temperature. (O=16, S=32,
Ca=40)
Answer: 2.4 x 10-5 mol2dm-6
3. The solubility of lead II chloride, PbCl2 is 0.016moldm3 at 298k.
Calculate the solubility product at this temperature.
Answer:1.6×10-5mol3dm-9
4. The solubility of calcium phosphate, Ca3(PO4)2 is 7.7× 10-4g/dm3
at 250c. Calculate the solubility product at this temperature. (O =16,
P =31,Ca=40)
Answer: 1.0×10-26mol5d.
5. Calculate the solubility in mol/dm3 of silver chloride, AgCl, at
298Kif its solubility product is 1.8×10-10 mol2dm-6
Answer: S = 1.3×10-5mol/dm3
6. Calculate the molar solubility of PbSO4 (lead II sulphate), given its
solubility product equal to 1.6×10-8.
Answer: 1.26×10-4M
7. Calculate the solubility in mol/dm3 of silverI sulphide, Ag2S at
298K if its solubility product is 6.3×10-51 mol3dm-9
Answer: S = 1.2×10-17moldm-3
8. Calculate the solubility in gdm-3 of chromium III hydroxide,
Cr(OH)3 at 250C if its solubility product is 1.0×10-33mol4dm-12(H=1,
O=16,Cr=52)
Answer: S = 2.47×10-9moldm-3
= 2.5×10-7g/dm3
QUIZ / 10 MARKS

1. The solubility of calcium carbonate CaCO3,

at 298K is 6.9×10-3 moldm-3. Calculate the
solubility product at this temperature.
2. Calculate the solubility in gdm-3 of
chromium (III ) hydroxide, Cr(OH)3 at 250C if
its solubility product is
1.0×10-33mol4dm-12(H=1, O=16,Cr=52)
 11.5. Definition and calculation of ionic
product (QC)
The ionic product (Q) of salt is the product of the concentrations of
the ions in solution raised to the same power as in solubility product
expression.

Consider the following salt MA that dissolves to give x cation M and y anions of A as
follows;

MxAy(s) xMy+ + yAx-

Q  [ M y  ]x [ A x  ] y
Qc=[My+]x[Ax-]y

Note: The ionic product describes concentrations that are not

necessarily equilibrium concentrations Whereas Ksp is applicable to
saturated solutions only.
Example:
Equal volumes of 0.2M lead nitrate and 0.4m potassium iodide solution are mixed, the ion
concentration are [Pb2+]=0.1M, [I-]=0.2M, calculate the ionic product.
Answer:
Pb(NO3)2(aq) + KI(aq) PbI2(s) + KNO3(aq)

PbI2(s) Pb2+ + 2I-

Q=[Pb2+][I-]2
=(0.1M)(0.2M)2
=0.004M3
Use of Qc for Predicting whether a salt
will precipitate or not

If Q>Ksp, salt will precipitate, the

solution is super saturated
If Q<Ksp, the salt does not precipitate,
the solution is not saturated
If Q=Ksp, the solution is saturated, we
are at equilibrium, the salt does not
precipitate
Example: Predict whether silver sulphate will precipitate when 1mL of 0.001M MgSO4(aq)
is poured to 100mL 0f 0.0005M AgNO3(aq). Ksp(Ag2SO4)=1.4×10-5

Answer:
MgSO4(aq) + AgNO3(aq) Mg(NO3)2(aq) + Ag2SO4(s)
Ag2SO4(aq) 2Ag+ + SO42-
Q=[Ag+]2[SO42-]

 0.50 103
[ Ag ] 
101103
 4.95  103 M
2 106
[ SO 4 ] 
101103
9.9 106 M
Q  (4.95  103 M ) 2 (9.9 10 6 M )
 2.4  10  12 M 3

Since Q< Ksp, no precipitate occurs.

EXERCISE
1. Will a precipitate of calcium hydroxide
form if 5.0 cm3 of ammonia solution
containing OH- ions with concentration of
2.0 × 10-3 mol/dm3 is added to 5.0 cm3 0f
0.05 mol/dm3 calcium chloride solution
CaCl2? (Ksp Ca(OH)2 = 5.5×10-6 mol3dm-9 at
298K.)

Annswer: Q = 2.5×10-8mol3dm-9
2. Mixing 35 ml AgNO3 0.01 M and 45 ml of HCl 0.1 M. Say if there will be a precipitate of
AgCl. Kps AgCl = 1.6.10-10.

Answer:
Number of moles of silver nitrate: n  M V  0.01 0.035  0.00035mol
Number of moles of HCl: n  M V  0.1 0.045  0.0045mol
New Volume  35  45  80ml  0.080l
n 0.00035
New [AgNO3]    0.004375M   Ag  
V 0.08
n 0.0045
New [HCl]    0.05625M  Cl  
V 0.08
The ionic product   Ag   Cl    0.004375  0.05625  2.46 10 4  1.6 10 10  K ps

So there will be a precipitate.

3. One adds a volume of 50 ml of 0.04 M Ca(NO 3)2 to 150 ml of a solution of (NH4)2SO4
0.008 M
a. Calculate the value of the product ion [Ca 2+]. [SO42-]
b. Is there a precipitate?
CaSO4 = 2.4 ksp. 10-5. [IN 2000]
Answer:
Number of moles of calcium nitrate: n  M V  0.04  0.05  2 103 mol
Number of moles of ammonium sulfate: n  M V  0.008  0.15  1.2 103 mol
New Volume  50  150  200ml  0.200l
n 2 103
New [Ca (NO3)2]    0.01M  Ca 2  
V 0.2
n 1.2 103
New [(NH4) 2SO4]    0.006M   SO42 
V 0.2
The ionic product  Ca 2    SO42   0.01 0.006  6 105  2.4 105  K ps

So there will be a precipitate.

11.6. Separation of ions by fractional
precipitation ( selective precipitation )
 Ions can be separated from each
other basing on the solubility of
their salts in water.
 This is done by using a reagent that
forms a precipitate with one or a
few of the ions in solution
(fractional precipitation or selective
precipitation ).
Examples
1. A solution containing both Ag+ and Cu2+; if
hydrochloric acid solution is added to this solution,
AgCl (Ksp=1.8×10-10) precipitates, while Cu2+ remains
in solution because CuCl2 is soluble. The reagent HCl
forms a precipitate with Ag+.
Ag+(aq) + Cl-(aq)↔ AgCl(s).

2. Fractional precipitation of a carbonate (CO3-2) and

a Chloride (Cl-).
A solution suspected to contain to contain a Chloride
and a carbonate is mixed with a solution of Silver
nitrate
A solution contains 1.0 x10-2 M Ag+ and 2.0 x10-2 M Pb2+ When CI- ion is added to the
solution, both AgCl (Ksp =1.8x10-10) and PbCl2 (Ksp =1.7x10-3) precipitate from the solution
What concentration of Cl- ions is necessary to begin the precipitation of each salt, and which salt
precipitates first?

Solution:

The salt requiring the lower concentration of CI- ions will precipitate out first. For AgCl we
have: Ksp [Ag+][Cl-] = 1.8 x 10 -10 Because [Ag+] =1.0x10 -10 M, the greatest concentration of
Cl- ions that can be present without causing precipitation of AgCl can be calculated from the Ksp
expression

Ksp =[1.0x10-2][Cl-] = 1.8x10 -10.

[Cl-] = =1.8x10-8 M. Any small Cl- concentration in excess to this will cause AgCl to
precipitate from solution.

For PbCl2 Ksp = [Pb2+][Cl-]2 =1.7x10 -5

[Cl-]2 = =8.5 x 10 -4 [Cl-] = =2.9x10-2 M.

Thus, the concentration of Cl- ions in excess of 2.9x10-2 will cause PbCl2 to precipitate.
Exercise
1. There is a solution containing
0.1M Zn2+ ions and 0.1M Ag+ ions
that we want to precipitate as
sulphides using H2S. Which of the two
sulphides will be the first to
precipitate? (ZnS: Kps = 1.2 x10-23
Ag2S: Kps = 1.6 x10-4
 11.7. Common ion effect and solubility
 It has known that the solubility of a sparingly
soluble ionic substance is obviously decreased in a
solution of another ionic compound when the two
substances have an ion in common.
This can be observed on the basis of the Lechatelier’s
Principle.

 Common ion Effect is the precipitation of a

sparingly soluble compound (or salt) from its
saturation by adding a soluble compound
containing one of the ions contained by the
sparingly soluble salt.
1. Calculate the solubility of calcium
sulphate in moldm-3 in
a) Water
b) Dilute sulphuric acid of
concentration 0.50 moldm-3
Ksp =2.4 x 10-5 mol2dm-6
Solution

a) If the solubility of calcium sulphate is ‘’s’’ moldm -3

[Ca2+] = smoldm-3and [SO42-] = Smoldm-3

Ksp = [Ca2+][SO42-]

2.4 x 10-5=S x S
.
S=

S =4.9 x 10-3moldm-3

[SO42-] = 0.50moldm-3

Ksp = [Ca2+][SO42-]

2.4 x 10-5 = S x 0.50

S= = 4.8 x 10-5 moldm-3

Solubility of CaSO4 decreases in the presence of sulphuric acid.

Example: Calculate the solubility of manganese sulphide :
(a) In water (b) in 0.01M of a solution of sulphide ions. Ksp (MnS) at 25oC is 2.5×10-
13
M
Answer: (a)
MnS(s) Mn2+ + S2-
Ksp = [Mn2+][S2-]
[ Mn 2 ]  [ S 2 ]  Ksp
 2.5 1013
 5 107 M
S ( MnS )  [ Mn 2 ]  [ S 2 ]
S ( MnS )  5 107 M
Exercises about Calculations on the common ion
effect
1. Calculate the solubility of calcium sulphate in moldm-3 in
a) Water
b) Dilute sulphuric acid of concentration 0.50 moldm-3
Ksp =2.4 x 10-5 mol2dm-6
Answer: (a) S =4.9 x 10-3moldm-3 (b) S = 4.8 x 10-5 moldm-3
2. The Ksp of PbSO4 is 1.6x10-8
a) Calculate the solubility of PbSO4 in
i. Water
ii. a 0.25M solution of Pb(NO3)2
b) conclude
Answer: (a)i. S= 1.26 x 10-4 ii. S=6.4x10-8 M
(b) The solubility of lead sulphate in pure water is
higher compared to the solubility of it in presence of a
common ion from lead nitrate;this illustrates the common
11.8. The pH and solubility
The term pH refers to the
concentration of [H ] ions in
+

solution.
The pH can be found if the [H ]
+

ions in a solution is known.

11.12. Complex ion formation and
solubility
If a sparingly soluble solid is placed in
contact with a solution containing a
ligand that can bind to the metal ion
much more strongly than H2O, then
formation of a complex ion will be
favored and the solubility of the solid
will be greater.
Example:
1. When ammonia is added to a solution of
copper (II) nitrate, in which the Cu2+ (aq) ion
is itself the complex ion
[M (H2O)4]2+aq +4NH3aq [M(NH3)4]2+ +4H2O Where M is a central metal ion.
11.9. Applications of solubility product
Some areas where solubility product is used:
a) Volumetric analysis: The concentration of Chloride ions
in a solution of soluble Chloride salt can be determined
by titration with a standard solution of silver nitrate
Potassium chromate is used as an indicator.
A white precipitate of silver Chloride forms first due to
lower solubility of silver Chloride
The end point is indicated by the formation of a red
precipitate of silver chromate This can be seen from the
solubility product (Ksp) value of silver chloride and silver
chromate. Ksp (AgCl = 1.2 x10 -10 mol2dm-6 Ksp (Ag2CrO4) =
2.4x10-12 mol2dm-9
Low concertation of Ag+ ions are needed to form a
precipitate with chloride ions than chromate ions .
b) Production of soap: saponification.
Brine concentrated solution of sodium chloride (NaCI) is added to the mixture of fats and oils
together with NaOH solution to precipitate out soap. Soap and sodium chloride are present in the
form of ions
Soap equilibrium: C17H35COO-Na+(s) C17H35COO- (aq) +Na+(aq)
When brine is introduced to the soap mixture, it introduces a common ion effect which effects
the equilibrium system in the backward direction. This is due to high concentration of sodium
ions (Na+) from sodium Chloride. As a result, the stearate ion (C 17H35COO-) combines with the
excess sodium ions to form soap which floats on top.
c) Depollution of water by removing toxic ions such
as heavy metals without precipitating others which
are essential for our body.
(Heavy metals : Arsenic copper, Barium, cadmium,
chromium,lead, mercury, Nickel, tholium, cobalt,
zinc,selenium,silver, antimony)

d) Purification of common salt (NaCl)

Common salt NaCl contains CaCl2 and MgCl2 as
impurities which makes it appear damp.
Pure common salt may be obtained buy bubbling
HCl gas into a saturated solution of impure NaCl,.
HCl provide Cl- which precipitate only CaCl2 and
e) Qualitative analysis
Ksp of some salt can be used to
identify them in their compounds
EX : Cl- is used to identify Ag+,Pb2+,
Hg+
 S2- is used to identify Hg2+,
Cu Cd
2+, 2+

 NH3 solution is used to identify

Mg Mn Fe Fe Al Cr Zn
2+, 2+, 2+, 3+, 3+, 3+, 2+,

2+, 2+, 2+
EXERCISES
1. One adds a volume of 50 ml of 0.04 M Ca(NO3)2 to 150 ml of a

solution of (NH4)2SO4 0.008 M

a. Calculate the value of the product ion [Ca2+][SO42-]

b. Is there a precipitate? Ksp CaSO4 = 2.4x10-5.

2. The silver chloride is very soluble in water. It is even less soluble in
dilute hydrochloric acid, but much more soluble in aqueous ammonia
(a) Explain how the solubility of AgCl is influenced by the addition
of:
i. Dilute HCl
ii. Aqueous ammonia
(b) The solubility product of silver chloride at 25°C is 1.44.10-10 mol2.
3. What is the solubility of Mg(OH)2 in
pure water? And in one liter of solution of
MgCl2 0.01 M? Ksp = 1.16. 10-11
Question 4
The solubility product of AgCl in water is 1.5 x 10-10. Calculate its
solubility in 0.01 M NaCl aqueous solution.
Question 5
At 298 K, the solubility of silver chloride in water is 0.00188 g L-1. What
is its Ksp?
Question 6
What is the solubility of Ag2CrO4 in water if the value of solubility
product, Ksp = 1.7 x 10-11(mol / L) 3.
Question 7
The concentration of Ca++ in blood is 0.0025M. If an oxalate solution
with oxalate ion concentration 1 x 10-7M is added to it, state whether
precipitation occurs or not. Solubility product of calcium oxalate = 2.3 x
10-9.
Question 8
A solution is prepared by mixing equal volumes of 0.01M MgCl2, and
0.02M MgC2O4 at 18°C. Would MgC2O4 precipitate out? Ksp of MgC2O4
-5
Question 9
Barium sulphate is sparingly soluble in water.
(a) Write an equation for the solubility of barium sulphate in water.
(b) Write an equation for the solubility product of barium sulphate.
(c) A saturated solution of barium sulphate contains 0.002563g per
litre of solution. Calculate the solubility product of barium sulphate.
(d) Calculate the solubility of BaSO4 in 1dm3 of 0.1M BaCl2 solution.
Question 10
Describe an experiment to determine the solubility product of
magnesium hydroxide.
Question 11
The concentration of Ca++ in blood is 0.0035M. If an oxalate solution
with oxalate ion concentration 1 x 10-6M is added to it, state
whether precipitation occurs or not. (Solubility product of calcium
oxalate = 2.3 x 10-9.)
Question 12
Will a precipitate form if 25.0 mL of 1.4 x 10-9 M NaI and 35.0 mL of 7.9
x 10-7 M AgNO3 are mixed? (Ksp for AgI at 25oC is 8.5 x 10-17)
Question 13
(a) Calculate how much strontium fluoride will dissolve in 1 L of water
given Ksp = 2.5 x 10-9 at 25oC.
(b) Will a precipitate form if 25.0 mL of 1.4 x 10-9 M NaI and 35.0 mL of
7.9 x 10-7 M AgNO3 are mixed? (Ksp for AgI at 25oC is 8.5 x 10-17)
Question 14
25.00 mL of saturated calcium hydroxide solution was titrated. It was
found that it reacted completely with 8.13 mL of 0.102 mol L HCl.
(a) Determine the solubility of Ca(OH)2 in grams per liter.
(b) Determine the Ksp of Ca(OH)2
Question 15
A saturated solution of Pb(OH)2 is filtered and 25.00 mL of this solution
is titrated with 0.000050 M HCl. The volume required to reach the
equivalence point of this solution is 6.70 mL. Calculate the
2+
Question 16
What is the solubility of sodium sulfate in 0.10 M strontium
nitrate? (Or, what is the minimum concentration of sodium
sulfate that would cause a a precipitate with 0.10 M
strontium nitrate?)
Question 17
The solubility of Pb(IO3)2(s) in a 0.10 M KIO3 solution is 2.6 x
1011 mol/L. Calculate Ksp for Pb(IO3)2(s).
Question 18
The Ksp for lead iodide (PbI2) is 1.4 x 108. Calculate the
solubility of lead iodide in 0.010 M NaI.
Question 19
Find [PbCl2] in a saturated solution of PbCl2. Ksp = 1.7 x 10-5.
Question20
Lead nitrate (Pb(NO3)2) is added to 0.010 M NaCl. Find the