Chapter 3:

Precipitation-solubility equilibrium
Chapter 2: Precipitation-Solubility Equilibrium
Mr N. HEBBAR
Chapter 3: Solubility-Precipitation Equilibria
1. Notion of solubility-saturation:
For any solute dissolved in a defined volume of solvent, there exists at a temperature
given a concentration limit, beyond which the body can no longer be dissolved, it is
the maximum concentration = the solubility.
Homogeneous Solution
Unsaturated solution
Saturated solution
Solid (Precipitate)
2. Definition of solubility:
The solubility in pure water of a chemical species is the maximum amount that can be
dissolve in 1L of pure water at the considered temperature. expressed in mol.L.-1ou g.L-1.
Examples at 20°C for ionic solids:
Sodium Chloride(s):
s = 6 mol/L1350g.L1.
Calcium hydroxide2(s)s=1.3102mol.L10.96 g.L1.
PbI2(s):
Silver chloride(s)
s = 1.35103mol.L1626 mg/L1.
s= 105mol.L11.4 mg/L1.
Examples at 25°C
for NaCl: s 6 mol.L-1= 352 g.L-1
NaCl is said to be very soluble.
AgCl is said to be very poorly soluble.
for AgCl: s 10-5mol.L-11.4 mg/L-1
A chemical species is considered to be poorly soluble when s < 10.2mol.L1.
Examples of slightly soluble ionic solids: AgCl, AgI, PbI2, CaCO3Fe(OH)3.
Solubility is reached when no more solid can be dissolved, and the solid then coexists.
with its ions in solution, the solution is said to be saturated and the undissolved solid is called
precipitated.
The saturated solution of an ionic compound is the site of the following heterogeneous equilibrium:
nCm+ + mAn
CnAm
The transformation in direction 1 is dissolution, the transformation in direction 2 is
precipitation, that is to say the crystallization of the solid within the solution.
Solubilitys is the concentration of solute CnAmin the saturated solution, that is to say the
maximum concentration of solute that can be dissolved at the given temperature.s
is expressed in molar concentration (mol.L-1) or massive (g.L-1). The concentrations
ionic ones result from:
[Cm+] =n×s
[An–= m×s
Solubility is independent of the mass of the solid phase in equilibrium with the solution.
saturated. The true solubility product of CnAmis the constant of this equilibrium written with the
Activities of species. The apparent solubility product Ksp, commonly used, is expressed
with the molar concentrations.
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Chapter 2: Precipitation-solubility equilibrium
MrN. HEBBAR
Ks depends on temperature and ionic strength. Ks is often formulated in the form of
pKs:
The more the compound is 'insoluble', the weaker Ks is, the higher the value of pKs.
3. Relationship between solubility product Ks and solubility s
By replacing [Cm+] and [An–in the previous formula by their expressions in terms of
We can express the solubility in water provided that no other reaction occurs.
superimposed on the solubility equilibrium:
Example 1:
Ag2CrO4
CaF2
Ks = 4 s3
Ks = 4 s3
Aluminum chloride3
Ks = 27 s4
Ks = 108 s5
Ca3(PO4)2
Example 2: pKs (MnS) = 12 and pKs (CuS) = 35.
Which of these two solids is the least soluble?
MnS(S) ⇄ Mn2+(aq)+ S2
.
Ks(MnS) = [Mn2+][S2] = 1012.
Ks(CuS) = [Cu2+][ S2] = 1035.
CuS is less soluble than MnS
(aq)
CuS(s) ⇄Cu2+(aq)+ S2
(aq)
Conclusion: The less soluble the precipitate, the smaller Ks is, and the larger pKs is.
But this rule must be used with caution.
Example 3:
pKs(Ag2Chromium(II) oxide4) = 12 > pKs(AgCl) = 10
It is, however, AgCl the least soluble. Indeed, the order of Ksp is not always that of the solubility.
It's what determines solubility.
Demonstration:
Cl
Silver chloride(s)
Ag+
(aq)
(aq)
Initial amount of substance in 1L
Amount of substance at equivalence in 1L
Concentration at equilibrium
n
n-s
0
s
s
0
s
s
Not defined (solid)
Ks(AgCl) = [Ag+Invalid input] =
= 103.1 sAgCl1.4 times 105mol.L1.
+
2
AgCrO4(s)
Chapter 2: Precipitation-Solubility Equilibrium
4. Condition to have a precipitate
Mr N. HEBBAR
A- Dissolution of a slightly soluble salt
Example: We add lime (Ca(OH)2(s)) in the water.
Two possibilities:
 The amount of substance per liter < s. Everything is dissolved, a liquid phase, no
precipitate.
Ca(OH)2(s) Ca2+(aq)+ 2OH
[Ca2+] < s et [OH] = 2[Ca2+< 2s.
(aq)
 The amount of substance per liter > s. Not everything is dissolved, we have a liquid phase +
a solid phase (a precipitate).
The liquid phase is a saturated solution.
Ca(OH)2(s)⇄ Ca2+(aq) + 2OH
(aq)
Ks = [Ca2+]eq× [OH]2
[Ca2+]eq = s and [OH]eq= 2s.
eq
B- Formation of a slightly soluble salt by mixing two solutions.
Three scenarios can be observed when mixing a solution.1containing a salt
totally soluble AB (AB
totally soluble CD (CD
A+ + B ) to a solutionS2containing also a salt
C+ + D):
1) If Pi = [A]+There is no rush obtaining a single phase.
2) If Pi = [A-] [B+We are on the verge of a storm. obtaining a saturated solution.
3) If Pi = [A]+Yes, there will be precipitation of salt. obtaining two phases: one phase
solid (precipitate) and a liquid phase (saturated solution, [A][B+= Ks).
The ionic product Pi= [A][B+] is an expression identical to the Ks but for which we
take the concentrations of the elements in the solution.
5. Existence diagram of a precipitate:
The previously established precipitation condition (Pi Ks) allows to trace some
diagram of precipitate existence.
Example: existence diagram of silver iodide AgI
To a solution of silver nitrate AgNO30.1 M, we add, without changing the volume, a
concentrated solution of potassium iodide KI. Determine the pI value for which there is
precipitation of AgI. Draw the existence diagram of the salt AgI as a function of pI.
Data: pKs(AgI) = 16.2; pI = log [I].

[Ag+] = [NO3= 0.1M
There is precipitation of Ag I when pi = [Ag+]  I]  Ks





For a solution of AgNO3of concentration 0.1 M:
In order to obtain a precipitate of AgI from the AgNO solution30.1 M, it is necessary that
Existence diagram of the precipitate AgI
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Chapter 2: Precipitation-solubility equilibrium
MrN. HEBBAR
6. Factors influencing the solubility of a compound
A- Influence of temperature
AnBm(s)
nAm+(aq) + mBn
: rH0
rH0enthalpy (energy) of dissolution
(aq)
. rH0< 0 : the reaction is exothermic
. rH0The reaction is endothermic
With a few exceptions, dissolution is endothermic.
We accept Van't Hoff's law
=
 LnKs(T2)  LnKs(T1) =
×(
)
R: constant of ideal gases
 Ks(T) is a monotonically increasing function with temperature.
Conclusion: Solubility usually increases with temperature.
B- Common ion effect
What is the behavior of a compound that is dissolved in a solution that contains
previously an ion of this compound?
For example, the dissolution of silver chloride in a hydrochloric acid solution.
of molar concentration 0.1 M. Hydrochloric acid being a strong acid dissociates
completely in H cations+ and anions ClSilver chloride dissociates according to
reaction
Silver chloride(s)

Ag+(aq)+ Cl
(aq)
Qualitatively, using Le Chatelier's principle, it is shown that the increase
chloride ion (thus to the right of the equilibrium) causes a shift of the equilibrium towards the
Left. The presence of chloride ions decreases the solubility of silver chloride.
Example:
In pure water (in 1 liter of solution), the solubility of silver chloride is:
Silver chloride(s)
AgCl(s)
n
Ag+(aq)+ Cl
(aq)
Cl
Chemical species
Ag+
t=0
t = tea
0
s
0
s
ns
Ks = [Ag+ ] × [Cl]  Ks = s × s = s2= 1.8 × 1010 s = 1.35 × 105mol/L
If silver chloride is dissolved in the 0.1 M hydrochloric acid solution, the situation
is as follows: in 1 liter of solution
AgCl(s)
Silver Chloride(s)
n
Chapter 2: Precipitation-Solubility Equilibrium
MrN. HEBBAR
The solubility of silver chloride in hydrochloric acid solution is lower than its
solubility in pure water. Verification of the calculation hypothesis: 1.8 × 109mol/L 0.1
mol/L. It was possible to make the approximation.
Attention: otherwise, if the approximation is not justified, that is to say if the two
terms are more or less of the same order of magnitude, we need to solve the equation of
second degree in order to determine solubility
C. pH effect
Example 1: case of silver acetate:
Reaction in the direction 1 Solubility increases
Réaction dans le sens 2La solubilité diminue
1
2

Ag(CH3CO2)(s)
Ag+(aq)+ CH3CO2 (aq)

CH3CO2 (aq) + H3O+
CH3CO2H + H2O


Ks = [Ag+] × [CH3CO2Ka =
;s = [Ag+] = [CH3CO2] + [CH3CO2H]


s = [Ag+] = [CH3CO2] +
=3CO2] × ( 1 +
)


[CH3CO2] =
 [Ag+] × [CH3CO2] = s × s = s ×
=
= Ks
s=
When the pH increases [H3O+decrease is decreasing
Example 2:
pH effect of the salt Zn(CN)2(s)
Zn(CN)2(s)⇄ Zn2++ 2CN
CN + H3O+  HCN + H2O
t=0
tea
Excess
0
0
t=0
teq
2s
x
0
Excess
Excess
Excesss
s
2s
Chapter 2: Precipitation-Solubility Equilibrium
MrN. HEBBAR
Exemple 3:
effect of pH of saltZn3(PO4)2(s) pKs= 32
3
2
Zn3(PO4)2(s) ⇄ 3 Zn2+(aq) +2 PO43
PO4+ H3O+  HPO4+ H2O
(aq)
2

HPO4+ H3O+  H2PO4+ H2O
t=0
gift
Excess
0
0

H2PO4+ H3O+  H3PO4+ H2O
Excesss
3s
2s
3 2
 solubility product ofZn3(PO4)2(s) :Ks = [Zn2+]3× [PO4]
 The constants: Ka1=
3s = [Zn2+]
; Ka2=
; Ka2 =
2s =
3s = [Zn2+]
+
+


2s =
(3s)3[Zn2+]3
(2s)2=

 (3s)3×(2s)2 =
×
×

 108 s5= Ks×

s=
Note:
Solubility increases when the concentration of
increase pH decreases
D. Complexation effect
One can significantly increase the solubility of a species in solution by forming a
complex.
For example, there is competition between the formation of silver chloride (precipitate) and
the diamine silver ion (complex ion):
Ag+(aq) +Cl−(aq)
Silver chloride(s)
Ag (NH3)2 (aq)
Chapter 2: Precipitation-solubility equilibrium
Mr N. HEBBAR
When ammonia is added to a saturated AgCl solution, a reaction occurs.
overall reaction:
+
Silver chloride(s)+2NH3(aq)
Ag (NH3)2 (aq) +Cl−
K=2×Ks = 10−2.55
(aq)
In the presence of an excess of ammonia, the constant K is low, the equilibrium is not greatly shifted.
to the right; there is redissolution of AgCl due to the formation of the diammine complex
silver (I). It is said that the complex masks the presence of AgCl.
Ag+(aq)+Cl−(aq)
Silver chloride(s)

Ks =10−9.75
+
Ag+(aq) +2NH3(aq)
Ag (NH3)2 (aq)
2=
= 107.2
Solubility is expressed by:
Let it be
solubility of AgCl in pure water
Digital application: for an NH solution31M
Conclusion: Solubility increases through complex formation
4× 102M (s= 105M)
7. Competitive precipitation:
Example 1: case of two precipitates corresponding to the same exchanged ion.
Couple: AgCl/Cl (pKs1= 10) and AgI/I (pKs116)
I reacts with Pb2+and the equilibrium (1) shifts in the direction (2) from where the disappearance of PbCl occurs2.
the balance sheet:
45
Chapter 2: Precipitation-Solubility Equilibrium
MrN. HEBBAR
Conclusion: For two competing precipitates, there is preferential precipitation.
the precipitate of Ks the smallest.
Example 2:
comparison of silver chloride (pKs = 9.75) with silver chromate (pKs = 12).
The two precipitates do not have the same stoichiometry, AgCl and Ag.2CrO4we cannot
compare their pKs directly. The competition reaction of the two precipitates is written as:
2−
(aq)
Ag2CrO4(s)+2Cl−
2AgCl(s) +CrO4
(aq)
of the constant:
The reaction constant being large, the equilibrium is strongly shifted in the direction of the
formation of AgCl. The addition of chloride ion in a saturated solution of silver chromate
leads to the dissolution of this solid with the preferential formation of silver chloride.
One can also reason by comparing their solubilities:
For AgCl
PourAg2CrO4
The solubility of silver chromate is higher than that of silver chloride. It is the
the least soluble salt that precipitates AgCl which precipitates.
8. Dosage of chloride ions by the Mohr method
It is a colorimetric assay that uses the selective precipitation of silver salts.
in relation to chloride and chromate ions.
To measure the chloride ions in an unknown solution, we add a few mL of a
potassium chromate solution at a given test point. One pours into the burette a
standard solution of silver nitrate. Silver ions precipitate preferentially with the
chloride ions following the reaction: Cl−(aq)+Ag+(aq) AgCl(s) (white precipitate)
When there are no more chloride ions in solution, the first drop of the nitrate solution
2-
excess silver reacts according to: CrO4 (aq) +2Ag+(aq)Ag2CrO4(s)red precipitate
The appearance of the red color allows for the detection of equivalence, silver chromate.
is the indicator of the end of the reaction.
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Chapter 2: Precipitation-solubility equilibrium
MrN. HEBBAR
Exercises
Exercise 1
In this exercise, we will neglect any acid-base reaction of the ions with water.
1. Establish a relationship between the solubility in pure water and the solubility product
Ks of
following compounds then calculate its value.
Manganese (II) iodate
Chromium (III) hydroxide Cr(OH)3
Mercury (II) cyanide Hg(CN)2
Mn(IO3)2
Zinc (II) phosphate Zn3(PO4)2
Silver(I) chromate Ag2CrO4
Lead(II) phosphate Pb3(PO4)2
[Link] on one axis the six values of delog s, and then, on another, the six values of delog Ks.
Conclude by ranking the six compounds in order of increasing solubility.
Mn(IO3)
6.3
Zn3(PO4)2
32.0
Cr(OH)3
31.0
Ag2CrO4
12.0
Mercury Cyanide2
35.1
Pb3(PO4)2
42.0
Composed
pKs
Exercise 2
A)Calculer la solubilitésdu chlorure de plomb PbCl2in pure water. Write the reaction of
dissolution, give the progress table
B) Plot the existence diagram of lead chloride when choosing Cl.− for particle
exchanged (pCl abscissa) with a concentration of Pb ion2+of 0.1mol/L.
C) Draw the existence diagram of lead chloride when choosing Pb2+for
exchanged particle (pPb abscissa) with a concentration of Cl ions− of 0.1mol/L.
We will demonstrate the position of the border for B and C. We give Ks(PbCl2=1,6.10-5.
Exercise 3
The solubility product of silver phosphate Ag3PO4Ks = 1016.
1. Determine the solubility of silver phosphate in pure water.
Determine the solubility of silver phosphate in a silver nitrate solution.
(AgNO3is completely dissociated) to 102mol.L1.
3. We mix 50 mL of a solution of Ag+ at 104mol.L1and 50 mL of a solution of ions
3
PO4to 104mol.L1What amount of silver phosphate material do we obtain?
4. We mix 30 mL of a solution of Ag+ to 102mol.L1and 20 mL of a solution of ions
PO43to 102mol.L1What quantity of silver phosphate material do we obtain?
Exercise 4
The solubility product Ks of silver carbonate Ag2CO3slightly soluble in water, is equal
at 8 1012The acidity constants Ka1and Ka2carbonic acid H2CO3valent


2
Chapter 2: Precipitation-Solubility Equilibrium
MrN. HEBBAR
B) If potassium chromate K is introduced2Chromium(II) oxide4in a saturated solution of sulfate
silver Ag2SO4containing an excess of solid, the latter, which is white, transforms into a
red solid consisting of silver chromate Ag2CrO4.
How can we explain this change in the nature of the solid phase in equilibrium with the
solution ? Data: Ks (Ag2SO4= 1.58×10-5
;
Ks (Ag2CrO4) = 1.12×10-12
Exercise 6
At what maximum pH should the water be acidified to form a sulfate solution?
gallium at 7.10-3mol.L-1to avoid the precipitation of gallium hydroxide Ga(OH)3?
Data: pKs (Ga(OH)335.7
EXERCISE 7
The shape of the diagram with its angular points A and B is characteristic of the phenomenon of
the disruption of balance represented by the appearance or disappearance of a precipitate.
In the presence of iodide ions, the Pb ions2+give a yellow precipitate and the Hg ions2+a
précipité rouge-orangé. Lorsqu’on ajoute goutte à goutte des ions Hg 2+in a test tube
containing a precipitate of lead iodide, the precipitate turns red-orange from the first moments
drops.
What can we conclude from this observation?
2) The document below corresponds to the simulation of the addition of a iodide ion solution to
an equimolar solution in Pb ions2+and Hg2+both at 0.100 mol/L. The graphs plotted
represent the percentage of metallic cations present in the solution as a function of pI
a) Identify the two curves plotted.
b) What do the angular points represent? Deduce the solubility products of PbI.2and HgI2.
c) Determine the equilibrium constant for the reaction that occurs when placed in the presence of
Hg ions2+with a precipitate of lead iodide.
48