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=+
.
Solubility

Salt reaction Ks = s= mol/L

AgIO3 AgIO3-Ag++IO- 3 s2 , . −

BaF2 BaF2-Ba2++2F- 4s3 , . −

Cr(OH)3 Cr(OH)3-Cr3++ 3OH- 27s4 , . −

Hg2(SCN)2 Hg2(SCN)2-Hg2+2+ 2SCN- 4s3 . −

Mourad AMARA
In this chapter, heterogeneous equilibria in aqueous solutions will be treated with
emphasis on the dissolution of salt and the conditions allowing its precipitation.

- Expression of the equilibrium constant denoted Ks

- Writing of salt dissolution reactions and calculations of solubilities

- Effects on solubility: temperature, pH ions in common

- Precipitation conditions
 EQUILIBRIUM CONSTANT
An equilibrium solubility of a solid in water can be considered in two ways:
- A dissolution giving rise to ions in solution
Example: silver chloride partially dissolves in water to give chloride (-I) and silver (+I)
ions:
+
AgCl(s) Ag +Cl- (1)

- A solvation equilibrium of a solid

Example: solid iodine is in equilibrium in water with solvated iodine:

I2(s) I2(aq) (2)

The equilibrium constant expresses the ratio of the concentrations of species dissolved in water,
considering the activity of a solid to be equal to 1.

Thus, we can write for the two equilibria respectively Ks (1) and Ks (2):
+
AgCl(s) Ag +Cl- (1) I2(s) I2(aq) (2)

1= +. − 2 = 2(

For a salt of general formula AxBy (s), dissolution in water allows us to write the general
solubility constant:

AxBy(s) xAy+(aq) + yBx-(aq)

= + . −
 Dissolution is obtained through solvation by water molecules oriented according to the polarity of the
species surrounded.

H
H O H H
O H O
O y+ x-
HAS H B
H H
O
H H
H
H O

The following table gives some values of solubility constants:

Compound BaSO4 Mg(OH)2 Hg2Cl2 PbI2 Ag2CrO4 SrCO3 CuBr Zn(CN)2 SrF2
Ks 1.1.10-10 5.6.10-12 1.4.10-18 9.8.10-9 1.1.10-12 5.6.10-10 6.3.10-10 8.0.10-12 4.3.10-9
 CALCULATION OF SOLUBILITY
The determination of the maximum solubility of a poorly soluble salt is mainly based on the value of its
equilibrium constant. The unit of measurement is mol/L, but can also be expressed in g/L.

Writing the dissociation equilibrium and the progress table allows you to quickly evaluate the relationship
between Ks and solubility.
CuBr(s) Cu+(aq) + Br-(aq)

Example 1 t = 0 VS0 0 0

teq VS0-s s s

The expression of the equilibrium constant taking into consideration the activity of the solid and its excess:

= +. −= . = 2

The solubility is then: = = , . − = , . − /

 To determine the solubility of PbI2(s) in water, The dissociation reaction is written:
Example 2

PbI2(s) Pb2+(aq) + 2I-(aq)

t=0 VS0 0 0

teq VS0-s s 2s

The equilibrium constant is written:

= 2+. − 2= . 2 2= 4 3

The solubility becomes:

3 3 9.8. 10−9
= = = 1.34. 10−3
4 4

Generally speaking, for a dissociation of a compound AxBy(s), the calculation is carried out from the Ks, such that:

= + . − = . = . +
- =+
.
 The calculation equation depends on the reaction:

Salt reaction Ks = s= mol/L

AgIO3 AgIO3-Ag++IO- 3 s2 1.76. 10−4
BaF2 BaF2-Ba2++2F- 4s3 6.29. 10−3
3

4
Cr(OH)3 Cr(OH)3-Cr3++ 3OH- 27s4 1.23. 10−8
4

27
Hg2(SCN)2 Hg2(SCN)2-Hg2+2+ 2SCN- 4s3 2. 10−7
3

4
 EFFECT OF COMMON ION
The solubility of a solid decreases after the introduction of an ion common to the solid compound.
This is justified by shifting the balance in the opposite direction so as to consume this addition.

Example 3
PbI2(s) Pb2+(aq) + 2I-(aq)
Let’s take the same example cited above, that of PbI2
t=0 excess 0 VS0
In a medium containing NaI (considered
teq excess if 2s'+C0
completely soluble ) of concentration C0
= 0.1M, the equilibrium becomes:
The excess means the weak dissolution of the solid.

The expression and the value of Ks being unchanged, we write: = 2+. − 2= ′. 2 ′+ 2 0

To simplify the solution of the equation, the necessary approximation2s'+C0≈ C0is justified, we therefore obtain = ′. ,
which gives for C0= 0.1M for example, ′= =
2 9.8.10(0.1
0
−9 2 =9.8. 10−7 /

We see that s' < s confirming the reduction in solubility under the effect of the common ion.
EFFECT OF TEMPERATURE
The temperature acts on the balance of salt dissolution according to the conditions of Van't
Hoff's law. The increase in temperature favors the endothermic sense.

- 1 1
ln s2= ln s1+ −
1 2

Most salt dissolution reactions are endothermic, requiring

heating to increase the dissolved quantities.

Endothermic reaction: when T - - Ks - - solubility “S” -

EFFECT OF PH
OH ions-are part of the composition of a large part of the poorly soluble salts, which is why the pH can
constitute a tool for controlling dissolution balances. Lechatelier's law of displacement of equilibria makes
it possible to follow the direction favorable to the addition or reduction of OH ions-.

Example 4 Mg(OH)2, Ks = 5.6.10-12

The solubility is calculated according to the dissolution equilibrium:

Mg(OH)2(s) - Mg2+ + 2OH-

= 2+. − 2= . 2 2= 4 3 which gives a solubility of1.12.10-4mol/L

And since[OH-] = 2s = 2.24.10-4mol/Lcorresponding topOH = 3.65or pH =10.35.

When pH > 10.35 - pOH < 3.65 - [OH-] > 10-3.65M, the reaction will move in the opposite
direction, precipitation of Mg(OH)2
 COMPETITIVE REACTIONS
When several salts co-exist in the same solution:The solid with the lowest solubility
value (deduced from Ks or pKs) is the one that dissolves last.

Example 5
Which dissolves first?

solubility(Ag2CrO4(Ks = 1.1.10-12)) <solubility(Ag2CO3(Ks = 8.5.10-12)) <solubility(Ag2SO4(Ks = 1.2.10-5))

Ag2SO4dissolves first (S -)

We notice that the solubility increases with the increase in Ks for salts
of the same chemical formulation

This is not the case between AgCl and Ag2CrO4, since the respective solubilities are

1.34.10-5mol/L < 6.5.10-5mol/Lwhile Ks (AgCl =1.8.10-10) > Ks (Ag2CrO4=1.1.10-12)

PRECIPITATION CONDITIONS
Precipitation is the reverse reaction of the dissolution of the solid in equilibrium with its ions: does the
mixture of two ions in solutions (cation + anion) necessarily lead to the precipitation of the solid?

this involves comparing the ionic product (product of concentrations) with the Ks in order to
locate the state of equilibrium or the state of saturation corresponding to the consumption of all
the water molecules used for the dissolution of the salt.

Furthermore, this ionic product was defined previously as being the quotient of the
reaction Q which expresses the concentrations of the non-equilibrium species.

- Q < Ks: the solution is unsaturated, no precipitation

We then have 3 possibilities:
- Q = Ks: the solution is saturated, there is equilibrium between the solid and the

- ions Q > Ks: the salt precipitates

 We mix 30mL of Pb(NO) 0.03M with 20mL of NaI 3.10-3M. We give Ks (PbI2) = 7.1.10 -9
32
Example 6
Is there precipitation of PbI2? Justify

To precipitate PbI2, the condition Q = 2+. [ −]2> must be respected.

After mixing, taking into account the dilution effect, the concentrations become
Cf=CiVi/Vf

0.03 .30 −
3. 10−3. 20
2+ = = 0.018 = = 0.0012
30 + 20 20 + 30

The ionic product: 2+. [ −]2= 0.018. (0.00122= 2.59. 10−8>

-There is precipitation of PbI2.

thank you