Module: Chemistry of Solutions (Semester 4)

2022-2023
Filière : Génie des Procédés Cycle : L.M.D Chapter 4: Solubility

Chapter 4 Solubility

I) Definition
The solubility of a compoundionicormolecular,calledsoluteis the maximum concentration
(enmolesbylitreof what compound can be dissolved or dissociated in asolventto a
given temperature. The solution thus obtained is thensaturated.
Example of the dissolution of sugar (molecular solid) in water.
MA (solid) M+(aqueous) + A-aqueous
at t = 0 C 0 0
at t = t≈ C S S
It is called solubility, its unit is either in mole/liter or in g/l.
The most common solvent is water. The solute can be a gas (for example: air in water), a
liquid (example: alcohol in water) or a solid (example: table salt NaCl in water).

II) Solubility constant

MA (solid) M+(aqueous) + A-(aqueous)
at t = 0 C 0 0
at t = t≈ C S S
S (Solubility) is the amount of MA dissolved

At this equilibrium corresponds the constant: K≈ =

M+ . A−
,K≈. MA . (solid) =KS
MA. (solid)
+ −
KS = M.A
Ksp solubility constant
In the case of an ionic solid compound, the equilibrium constant of the dissolution reaction
is calledsolubility productand is rated Ks(T)It only depends on the temperature T and in
In general, it increases with this. Solubility S depends on this solubility product and varies.
in the same direction.
A) Expression of solubility product
MA (solid) MA (dissolved) M+(solvated) + A-(solvated)
M+ . A −
K≈ =
+ −
K≈. MA. = M.A
(dissolve)
MA. (dissolve)
The solubility product (Ksp)S) is theequilibrium constantcorresponding to the dissolution of a
solid in asolvent.
PS= K≈. MA. + −
= M.A.
(dissolve)
.
General case: MxAy(solid) xMy+(solvate) + yAx-solvate
x y
KS = My+ . A x− pKs = -logKs
examples of numerical values of the solubility product in water at 25 C
In order of decreasing solubility
Note: The solubility product value depends on the temperature. In general, it increases.
with the temperature.

Formula Name Ks

NaCl Chloridesodium 38.98

NiCO3 CarbonateofNickel 1,3 . 10-7
Calcium hydroxide
Hydroxideofcalcium
2 5.5 . 10-6
Cu(OH)2 Hydroxide ofcopper 2.2 . 10-20
Mercury sulfideSulfur ofmercury 4 . 10-53

Chemistry of Solutions Course (S4 LMD2022/2023). Page No. 1 /7 Performed by Prof. Rachid Fitas
 Module: Chemistry of Solutions (Semester 4)
2022-2023
Field: Process Engineering Cycle: L.M.D Chapter 4: Solubility

B) Solubility and Solubility Product.

In a solution containing ions A- and M+, the comparison between the solubility product
([A-.[ M+) and the solubility constant Ks allows us to know if there is precipitation or not.
a) Si [A-]. M+]< Ks the solubility limit is not reached, there is no precipitation
b) If [A-] .[ M+]> Ks There will be a solid MA precipitation until the Ps verifies the equality.

1- Relationship between Molar Solubility and Solubility Product.

a) Example of an ionic compound of type XY: CuBr.
Copper bromide dissolves in water according to the following equilibrium:
Copper(I) bromide Cu+ + Br-
Let s be the solubility of copper bromide. Dissolving s moles per liter of CuBr gives s.
moles per liter of Cu+ and s moles per liter of Br-We can describe the situation in the following way
next :
CuBr Cu+ + Br-
at t = 0 S 0 0
at t = t≈ 0 S S
The product of CuBr of copper is written:
½
KS= [Cu+] . [Br-] = S . S = S2KS= S2. S= (KS)
KS[Cu+] . [Br-] = 5,3.10-9S= (5,3.10-9)½ S = 7.2 × 10-5mole/l
MCopper(I) bromide= 63.55 + 79.90 = 143.45 [Link]- 1,
The mass solubility of copper bromide is S.m1.03.10-2g/l.

b) Example of an ionic compound of type X2Y: Example Ag2CO3.

Silver carbonate2CO3Silver dissolves according to the balance:
Ag2CO3 2Ag+ + CO3 2-
Let s be the solubility of Ag.2CO3The dissolution of s moles of AgCO3give 2s mole of Ag+ and s mole
-
of CO3The situation can be described as follows:
2-
Ag2CO3 2Ag+ + CO3
at t = 0 S 0 0
at t = t≈ 0 2S S

The solubility product of AgCO3is written:

KS
KS= [Ag+] 2. [CO3] 2-
= (2S)2. S = 4S3KS= 4S3. S= (KS/4) ½ S= 3
4
8.1.10−18
KS= 8,1.10-18 S= 3 S = 1.26 * 10-6mole/l
4
M=275.7 g/mole, the mass solubility Sm= 1.26.10-6.275.7=3.49.10-4g/l.
c) Generalization: An ionic compound with the general formula XaYb
The dissolution of the ionic compound with the general formula XaYbis written:
XaYb aXb+ + bYa-
The dissolution of s moles of XaYbgive the moles of Xaand b s mole of YbWe can describe the situation.
in the following manner:
XaYb aXb+ + bYa-
at t = 0 S 0 0
at t = t≈ 0 aS bS

Chemistry of Solutions Course (S4 LMD 2022/2023). Page no. 2 /7 Performed by Pr. Rachid Fitas
 Module: Chemistry of Solutions (Semester 4)
2022-2023
Field: Process Engineering Cycle: L.M.D Chapter 4: Solubility

KS
KS= [Xb+]a. [Ya-]b(aS)a. (bS)b= (a)a. (b)bSa+b. S= (KS(a)a. (b)b)1/a+b S= a+b
a a .bb
2-Effect of the common ion on solubility.
What is the behavior of a compound that is dissolved in a solution that contains an ion of it?
composed?
example the dissolution of silver chloride in a solution of hydrochloric acidof
molar concentration 0.1 M. Hydrochloric acid being astrong acidcompletely dissociates into
cations H+ and anions Cl-Silver chloride dissociates according to the reaction:
AgCl Ag+ + Cl-
Qualitatively using theLe Chatelier's principle, it shows that the increase of ion
chloride (thus to the right of the equilibrium) causes a shift of the equilibrium to the left. The
The presence of chloride ions decreases the solubility of silver chloride.
AgCl ⎯⎯⎯⎯→
⎯ Ag+ + Cl−
In pure water, the solubility of silver chloride is:
AgCl Ag+ + Cl-
at t = 0 S 0 0
at t = t≈ 0 S S
½
KS= [Ag ] . [Cl ] = S. S = S , KS= S . S= (KS) KS(AgCl)= 1,8.10-10 S= (1,8.10-10)½
+ - 2 2

S=1.35 x 10-5mole/l
If silver chloride is dissolved in the 0.1 M hydrochloric acid solution, the situation is as follows
next :
AgCl Ag+ + Cl-
at t = 0 S’ 0 0.1
at t = t≈ 0 S’ S’+0.1
KS= [Ag ] . [Cl ] = S’. (S’+0,1) = 1,8.10 S'«0,1→ S'+0.1 ≈ 0.1.
+ - -10

KS= S'. 0.1 = 1.8.10-10S'≈1.8·10-9mole/l. S'<S

The solubility of silver chloride in a hydrochloric acid solution is lower than its
solubility in pure water. Verification of calculation hypothesis 1.8.10-9mole/l<0.1 It was possible
to make the approximation.
The solubility of a salt is decreased if an ion of that salt is already present in the solution: this is called
thisthecommon ion effect.
3- Precipitation of two or more ions by the same ion.
Solution containing a concentration C1in ion Cl- and C2in ion Br-we add AgNO3 (Ag+)
solid without changing the volume. In what order will the precipitates of AgCl and AgBr appear.
KS(AgCl)= [Ag+].[Cl-] ; KS(AgBr)=[Ag+].[Br-The 2 salts coexist in the solid state (at certain moments)
KS(AgCl)= 2.10-10; KS(AgBr)= 4.10-13. KS(AgCl)/KS(AgBr)[Cl-] / [ Br-= 5.102.
We can consider 3 possibilities.
a) If C1= 500C2Cl- and Br- simultaneously plunge from the 1eradrop of AgNO3added.
b)- If C1< 500C2AgBr precipitates alone until [Br-has sufficiently decreased to
check the relationship (1). At this moment, AgCl precipitates at the same time as AgBr and in such proportions
that equation (1) remains verified.
c)- If C1500C2AgCl which precipitates first until [Cl-allows to verify
the equation (1)
Special case:
If C1= C2It is AgBr that precipitates first and in this case we can determine [Br-] to
the moment when AgCl will start to precipitate. At that moment [Cl-=C, therefore [Br-=C/500. There is left
so more than 1/500thfrom the initial concentration of Br-.

Chemistry of Solutions Course (S4 LMD 2022/2023). Page No. 3 / 7 Carried out by Prof. Rachid Fitas
 Module: Chemistry of Solutions (Semester 4)
2022-2023
Field: Process Engineering Program: LMD Chapter 4: Solubility

Equal concentrations in Ag+ and I- (KS(AgI)= 10-16)

KS(AgCl)/KS(AgI)[Cl-] / [ I-= 2.10-6let [I-] = C/2.106when AgCl starts to precipitate
practically all the iodide is precipitated.
This presents an important interest for the selective separation of halides by precipitation.
successive by AgNO3.

4- Influence of pH on the Solubility of slightly soluble electrolytes.

An ion of an insoluble electrolyte can react with H ions.3O+ or OH- a soluble compound and
Little dissociated: The insoluble electrolyte will tend to dissolve by the addition of H ions.3O+ or OH- (He doesn't
will not precipitate in sufficiently acidic or basic medium.
Several cases are conceivable:
If A- of an insoluble salt MA, is the conjugate base of a weak acid, the addition of H3O+ au
the average of a strong acid will give:
MA M+ + A-
A- + H3O+ AH + H2O
The lower the pH (strong acid), the more... the solubilisation of MA is moved
Conclusion: A poorly soluble salt of weak acid becomes soluble in a strong acidic environment.
2) A poorly soluble hydroxide of the type MOH tends to dissolve in a strong acidic medium due to
of poorly dissociated HOH formation.
MOH M+ + OH-
OH- + H3O+ HOH + H2O
If this hydroxide is amphoteric, it dissolves in a basic medium:
MOH MO- + H+
H+ + OH- H2O
3) The soluble salt of a metal M whose hydroxide MOH is amphoteric.
MA M+ + A-
M+ + OH- MOH MO- + H+
H+ + OH- H2O
4) A poorly soluble AH acid dissolves in a basic solution by forming HOH very
little dissociated.

HA A- + H+
H+ + OH- H2O
5) Examples:
a) Dissolution in an acidic medium of a salt of a weak acid: example: nitrites, oxalates,
sulfides, chromates, phosphates.
- -
Silver nitrate2Silver nitrate2 Ag+ + NO2Ks = [Ag NO2]
+

NO2-+ H3O+ HNO2+ H2O

NO2− . H 3O +
Ka =
HNO2 .
-
• In pure water: [Ag+NO2].
• In acidic medium: [Ag+] = [NO2- ] + [HNO2. . [Ag=+
[NO2 ] (1- + [H3O+]/Ka).
[Ag+]2= Ks (1 + [H3O+]Ka). [Ag+] = S = (Ks (1 + [H3O+]/Ka)) . ½
10− pH
S = Ks(1+ )
Ka

Chemistry of Solutions Course (S4 LMD2022/2023). Page number 4 / 7 Made by Prof. Rachid Fitas
 Module: Chemistry of Solutions (Semester 4)
2022-2023
Field: Process Engineering Cycle: L.M.D Chapter 4: Solubility

b) the influence of pH on the solubility of slightly soluble electrolytes

Ag2C2O4(to be done by the students)
2) Ca3(PO4)2(to be done by the students)
Ks 10− pH10−2pH
a) Ag2C2O4: S= 3 (1+ + )
4 Ka2 Ka2Ka1
2-
Ag2C2O4 2Ag+ + C2O4 Ks = [Ag+]2.[ C2O4]2-
C 2 O 42- . H 3 O + C 2 O 42- . H 3 O +
C2O42-
+ H3O+ HC2O4+ H2O- Ka1 = HC2 O −4 . =
HC2 O 4− . Ka1
HC2 O-4 . H 3O + HC2 O -4 . H 3 O +
HC2O4-+ H3O+ H2C2O4+ H2O Ka2 = H 2 C 2 O4 =
H 2C2O4 . Ka2
• In pure water: [Ag+] = 2[C2O4]. 2-
• In an acidic environment:

[Ag+] =2([C2O4]2-+ [HC2O4] +- [H2C2O4]).

C 2 O 42- . H 3 O + HC2O -4 . H 3 O +
Ag+] = 2([C2O4] 2-+ + )
Ka1 Ka 2
C 2 O 42- . H 3 O + C 2O 42- . H 3 O + . H 3 O +
[Ag+] = 2([C2O4]2-+ + )
Ka1 What1 Ka 2
2
C 2 O 42- . H 3 O + C 2 O 42- . H 3 O +
Ag+] = 2([C2O4] 2-+ + )
Ka1 Ka2Ka1
C 2 O 42- .10− pH C 2 O 42- .10−2pH 10− pH 10−2pH
[Ag+] = 2([C2O4]2-+ + 2-
) → [Ag+] = 2([C2O4(1 + + )
Ka1 Ka2Ka1 Ka1 Ka 2Ka1
10− pH
+ 10
−2pH
Ks = [Ag+]2. [ C2O4]2-; +
[ Ag ] [Ag+]2= 2[Ag+]2C2O41 + 2-
).
Ka1 Ka 2Ka1
10− pH 10−2pH
[Ag+]3= 2[Ag+]2[C2O4(12- + + )
Ka1 Ka 2Ka1
10− pH 10−2pH 10− pH 10−2pH
[2S]3= 2Ks (1 + + ) → 8S3= 2Ks (1 + + )
Ka1 Ka 2Ka1 Ka1 Ka 2Ka1
1
Ks 10− pH 10−2pH Ks 10− pH 10−2pH
S= (1 + + ) → S= ( (1 + + ))
3
3
4 Ka1 Ka 2Ka1 4 Ka1 Ka 2Ka1

Ks 10− pH10−2pH
→S=3 (1+ + )
4 Ka2 Ka2Ka1
b) Ca3(PO4)2(to be done by the students)

Ks 10− pH10−2pH 10−3 pH

S=5 (1+ + + )2
108 Ka3Ka2 Ka3Ka1 Ka2 Ka3

3-
Ca3(PO4)2; Ca3(PO4)2 3Ca2++ 2PO4 Ks = [Ca2+]3.[PO4]3 - 2

PO34- . H 3 O + PO34- . H 3 O +
PO43-
+ H3O+ HPO4+ H2O2- Ka1= → HPO42− . =
HPO42− . What1
HPO42- . H 3 O + HPO42- . H 3 O +
HPO42-
+ H3O+ -
H2PO4+ H2The Ka2= → H 2PO −4 =
H 2PO −4 . Ka 2
H 2PO −4 . H 3 O + H 2PO −4 . H 3 O +
H2PO4-+ H3O+ H3PO4+ H2O Ka3= → H 3 PO4 =
H 3 PO4 Ka3
3- 3 - 2
• In pure water: [Ca = 3S ; [PO4= 2S ; Ks = [Ca ] .[PO4]
2+ 2+ 3
.
• In an acidic environment:
3-
• Ca3(PO4)2 3Ca2++ 2PO4 Ks = Ca2+ . PO3-4
3 2

Course on Solution Chemistry (S4 LMD2022/2023). Page n° 5 / 7 Produced by Pr. Rachid Fitas
 Module: Chemistry of Solutions (Semester 4)
2022-2023
Field: Process Engineering Cycle: L.M.D Chapter 4: Solubility

• 3S 2S 2 Ca2+ = 3 PO34-
2 Ca2+ = 3( PO34- + HPO42- + H 2 PO−4 + H3PO4 )
PO34- . H 3O + HPO42- . H 3O + H 2PO −4 . H 3O +
2 Ca2+ = 3( PO34- + + + = ).
Ka1 Ka2 Ka3
PO34- . H 3O + PO34- . H 3O + . H 3O + HPO42- . H 3O + H 3O +
2 Ca2+ = 3( PO34- + + + ).
Ka1 Ka1 Ka2 Ka2 Ka3
PO34- . H 3O + PO34- . H 3O + . H 3O + PO34- . H 3O + . H 3O + H 3O +
2 Ca2+ = 3( PO34- + + + ).
Ka1 Ka1 Ka2 Ka1 Ka2 Ka3
2 3
PO34- . H 3O + PO34- . H 3O + PO34- . H 3O +
2 Ca2+ = 3( PO34- + + + ).
Ka1 Ka2Ka1 Ka3Ka2Ka["1"]
2 3
. H 3O + . H 3O + . H 3O +
2 Ca2+ =3 PO34- (1+ + + ).
Ka1 Ka2Ka1 Ka3 Ka2What1
10− pH 10−2pH 10−3 pH
2 Ca2+ = 3 PO34- (1+ + + ).
Ka1 Ka2Ka1 Ka3 Ka2Ka1
10− pH 10−2pH 10−3 pH
( 2 Ca2+ )2= (3 PO34- (1+ + + ))2.
What1 Ka2Ka1 Ka3 Ka2Ka1
10− pH 10−2pH 10−3 pH
→ 4 Ca2+ = 9 PO34- (1+ + + )2.
2 2

Ka1 Ka2Ka1 Ka3 Ka2Ka1

10− pH 10−2pH 10−3 pH
= 9 Ca2+ (1+
2
+ + )2.
5 3
4 Ca2+ PO34-
Ka1 Ka2Ka1 Ka3 Ka2Ka1
10− pH 10−2pH 10−3 pH
4(3S)5= 9Ks(1+ + + )2.
Ka1 Ka2Ka1 Ka3 Ka2Ka1
10− pH
+ 10 10−3 pH
−2pH
→ 4.35.S5= 32Ks(1+ + )2.
Ka1 Ka2Ka1 Ka3 Ka2Ka1
10− pH 10−2pH 10−3 pH
4(33S)5= Ks (1+ + + )2.
Ka1 Ka2Ka1 Ka3 Ka2Ka1
10− pH 10−2pH 10−3 pH
→ 108S5= Ks(1+ + + )2.
Ka1 Ka2Ka1 Ka3 Ka2Ka1
Ks 10− pH 10−2pH 10−3 pH Ks 10− pH 10−2pH 10−3 pH
S 5= (1+ + + )2. S=( (1+ + + )2 )
1
5

108 Ka1 Ka2Ka1 Ka3 Ka2Ka1 108 Ka1 Ka2Ka1Ka3 Ka2Ka1

Ks 10− pH 10−2pH 10−3pH
S= 5 (1+ + + )2 End of Chapter
108 Ka3 Ka2Ka3What1 Ka2What3

Solution Chemistry Course (S4 LMD2022/2023). Page number 6 / 7 Created by Prof. Rachid Fitas