18 Chapter 18 Solubility

GENERAL CHEMISTRY
PRINCIPLES AND MODERN APPLICATIONS

ELEVENTH EDITION
PETRUCCI HERRING MADURA BISSONNETTE
Solubility and
Complex-Ion Equilibria 18
PHILIP DUTTON
UNIVERSITY OF WINDSOR
DEPARTMENT OF CHEMISTRY AND BIOCHEMISTRY
Slide 18 - 1 General Chemistry: Chapter 18 Copyright © 2017 Pearson Canada Inc.

Additional Aspects of CONTENTS
Acid-Base Equilibria 18-1 Solubility Product Constant, Ksp

18-2 Relationship Between Solubility
and Ksp
18-3 Common-Ion Effect in Solubility

Equilibria
18-4 Limitations of the Ksp Concept

18-5 Criteria for Precipitation and Its
Completeness
18-6 Fractional Precipitation

18-7 Solubility and pH
18-8 Equilibria Involving Complex Ions
18-9 Qualitative Cation Analysis

18-1 The Solubility Product Constant, Ksp
The equilibrium constant for the equilibrium established
between a solid solute and its ions in a saturated solution.
CaSO4(s) Ca2+(aq) + SO42−(aq)
Ksp = [Ca2+][SO42−] = 9.1×10−6 at 25°C

18-2 The Relationship Between Solubility and Ksp
Molar solubility.
The molarity in a saturated
aqueous solution.
Related to Ksp
EXAMPLE 18-2
g CaSO4/100 mL → mol CaSO4/L

→ [Ca2+] and [SO42−]
Barium sulfate, BaSO4, is a good
→ Ksp = 2.3×10 −4 absorber of X-rays.
The result is too large because conc was used instead of a

How many g of BaSO4 can be dissolved in 1.00 L of
water?
Ksp = [Ba2+][SO42-] = 1.110-10 at 25°C
Slide 6 of 32 General Chemistry: Chapter 18 Copyright © 2011 Pearson Canada Inc.

water?
Ksp = [Ba2+][SO42-] = 1.110-10 at 25°C

water?
Ksp = [Ba2+][SO42-] = 1.110-10 at 25°C

water?
Ksp = [Ba2+][SO42-] = 1.110-10 at 25°C

water?
Ksp = [Ba2+][SO42-] = 1.110-10 at 25°C

water?
Ksp = [Ba2+][SO42-] = 1.110-10 at 25°C

How many g of Fe(OH)3 can be dissolved in 1.00 L of
water? K = [Fe3+][OH-]3 = 410-38 at 25°C
sp

water? K = [Fe3+][OH-]3 = 410-38 at 25°C
sp

water? K = [Fe3+][OH-]3 = 410-38 at 25°C
sp

water? K = [Fe3+][OH-]3 = 410-38 at 25°C
sp

water? K = [Fe3+][OH-]3 = 410-38 at 25°C
sp

Which has the higher molar solubility Mg3(PO4)2 (Ksp
= 1 x 10-25) or AgI (Ksp is 8.5 x 10-17)

Which has the higher molar solubility Mg3(PO4)2 (Ksp
= 1 x 10-25) or AgI (Ksp is 8.5 x 10-17)

18-3 The Common-Ion Effect in Solubility
Equilibria
The solubility of a slightly soluble ionic compound is lowered in the

presence of a second solute that furnishes a common ion.

FIGURE 18-1
The common-ion effect in solubility equilibrium

18-4 Limitations of the Ksp Concept
Ksp is usually limited to slightly soluble solutes.
• For more soluble solutes we must use ion activities
• In ionic solutions of moderate to high concentrations activities and
concentrations are generally far from equal.
The Diverse Noncommon Ion Effect: The Salt Effect
• Ionic interactions are important even when an ion is not apparently

participating in the equilibrium.
• The effect of “noncommon” or diverse ions tend to increase rather
than decrease solubility.

FIGURE 18-2
Comparison of the common-ion effect and the salt effect on the molar solubility of Ag 2CrO4

The assumption that ions are completely dissociated in
solution is often not valid.
Some ions join together in ion pairs.

Held together by electrostatic interactions.
Increasingly likely as charges on ions increase.
Measured solubility of MgF2 is 4×10−3 M

Cannot assume that [Mg2+] is 4×10−3 M
and that of [F−] is 8×10−3 M

Incomplete Dissociation of Solute into Ions
An ion pair, in a magnesium fluoride aqueous solution. The water molecules

surrounding the ion pair form what is referred to as a solvent cage.

Simultaneous Equilibria
Other equilibria are usually present in a solution.
Kw for example.
Reactions between solute ions and other species.
Acid base reactions.
Complex-ion formation
These must be taken into account if they affect the

equilibrium in question.

The dissolution of PbI2(s) is more complex than we have shown:
PbI+(aq) + I−(aq)
−I− −I−
PbI42−(aq) PbI3 −(aq) PbI2 (s) Pb2+(aq) + 2 I−(aq)
+I− +I−
PbI2 (aq)

Assessing the Limitations of Ksp
Concentrations are usually substituted for activities.
Conflicting results are obtained as a result.
Useful predictions can still be made.

18-5 Criteria for Precipitation and Its
Completeness
AgI(s) Ag+(aq) + I−(aq)
Ksp = [Ag+][I−] = 8.5×10−17
Mix AgNO3(aq) and KI(aq) to obtain a solution

that is 0.010 M in Ag+ and 0.015 M in I−.
Saturated, supersaturated or unsaturated?
Q = [Ag+]init×[I−] init = (0.010)(0.015) = 1.5×10−4 > Ksp

The ion product, Qsp
Qsp > Ksp Supersaturated, precipitation should occur.

Qsp < Ksp Unsaturated, precipitation cannot occur.
Qsp = Ksp Saturated, the solution is at equilibrium.

FIGURE 18-3
Applying the criteria for precipitation from solution – Example 18-5 illustrated

18-6 Fractional Precipitation
FIGURE 18-4
Fractional precipitation-Example 18-7 illustrated

Selective Precipitation
An aqueous solution that is 2.00 M in AgNO3 is slowly

added from buret to an aqeous soluton that is
0.0100M in Cl- and also 0.0100 M in I-.
Is separation of the two ions by selective precipitation

feasible?
KspAgCl = 1.8 x 10-10, KspAgI = 8.5 x 10-17

pH can affect the solubility of a salt.

Especially when the anion of the salt
is the conjugate base of a weak
acid.
Mg(OH)2
Milk of Magnesia.

Mg(OH)2 (s) Mg2+(aq) + 2 OH−(aq) (18.2)
OH−(aq) + H3O+(aq) 2 H2O(l) (18.3)

Mg(OH)2 (s) Mg2+(aq) + 2 OH−(aq) Ksp = 1.8×10−11
2 OH−(aq) + 2 H3O+(aq) 4 H2O(l) K' = (1/Kw)2 = 1.0×1028
Mg(OH)2(s) + 2 H3O+(aq) Mg2+(aq) + 4 H2O(l) (18.4)
K = Ksp(1/Kw)2 = (1.8×10−11)(1.0×1028) = 1.8×1017

18-8 Equilibria Involving Complex Ions
AgCl(s) + 2 NH3(aq) → [Ag(NH3)2]+(aq) + Cl−(aq) (18.5)
FIGURE 18-5
Complex-ion formation: dissolution of AgCl(s) in NH3

A complex ion is a polyatomic cation or anion composed of a
central metal ion to which ligands are bonded.
Coordination compounds are substances containing

complex ions

Formation constant, Kf
AgCl(s) + 2 NH3(aq) → [Ag(NH3)2]+(aq) + Cl−(aq) (18.5)
It helps to think of this reaction as two simultaneous equilbria.
AgCl(s) Ag+(aq) + Cl−(aq) (18.6)
Ag+(aq) + 2 NH3(aq) [Ag(NH3)2]+(aq) (18.7)
[[Ag(NH3)2]+]
Kf = = 1.6×10 7
[Ag+][NH3]2

7

7

7

Slide 18 - 73 General Chemistry: Chapter 18
Copyright © 2017 Pearson Canada Inc.
18-9 Qualitative Cation Analysis
An analysis that aims at identifying the cations present in a
mixture but not their quantities.
We think of cations in solubility groups according to the
conditions that causes precipitation.
Group 1: chloride group (HCl)
Group 2: hydrogen sulfide group (H2S)
Group 3: ammonium sulfide group (NH3, NH4+)
Group 4: carbonate group (CO32−)
Group 5: soluble group
Selectively precipitate the first group of cations then move on to
the next.

FIGURE 18-7
Outline of a qualitative
cation analysis

Cation Group 1: The Chloride Group
(a) Group 1 precipitate
Wash ppt with hot water. PbCl2 is slightly soluble.
Test aqueous solution with CrO42−.
Pb2+(aq) + CrO42− PbCrO4(s)
Test remaining precipitate with ammonia.
AgCl(s) + 2 NH3(aq) Ag(NH3)2 (aq) + Cl−(aq)
Hg2Cl2(s) + 2 NH3(aq) Hg(l) + HgNH2Cl(s) + NH4+(aq) + Cl−(aq)

Dark gray

Cation Groups 2 and 3:
Equilibria Involving Hydrogen Sulfide.
H2S, hydrogen sulfide or hydrosulfuric acid, is a
weak diprotic acid
H2S(aq) + H2O(l) H3O+(aq) + HS−(aq) Ka1 = 1.0×10−7
HS−(aq) + H2O(l) H3O+(aq) + S2−(aq) Ka2 = 1×10−19
S2− is an extremely strong base and is unlikely to be the

precipitating agent for the sulfide groups.

S2−(aq) + H2O (l) HS−(aq) + OH−(aq)
Kb = Kw/Ka2 = (1.0×10−14/1×10−19) = 1×105

PbS(s) + H2O(l) Pb2+(aq) + HS−(aq) + OH−(aq) Ksp = 3×10−28
H3O+(aq) + HS−(aq) H2S(aq) + H2O(aq) 1/Ka1 = 1.0/1.0×10−7
H3O+(aq) + OH−(aq) H2O(l) + H2O(l) 1/Kw = 1.0/1.0×10−14
PbS(s) + 2 H3O+(l) Pb2+(aq) + H2S(aq) + 2 H2O(l)
Ksp 3×10−28
Kspa = = = 3×10−7
Ka1×Kw 1.0×10−7 ×1.0×10−14

Dissolving Metal Sulfides
Several methods exist to re-dissolve precipitated metal

sulfides.
React with an acid.
FeS readily soluble in strong acid but PbS and HgS
are not because their Ksp values are too low.
React with an oxidizing acid.
3 CuS(aq) + 8 H+(aq) + 2 NO3−(aq) 3 Cu2+(aq) + 3 S(s) + 2 NO(g) + 4 H2O(l)
(18.9)
[Cu(H2O)4]2+(aq) + 4 NH3(aq) → [Cu(NH3)4]2+(aq) + 4 H2O(l)

Pale blue Deep violet

FIGURE 18-9
Complex-ion formation: A test for Cu2+(aq)

End of Chapter

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GENERAL CHEMISTRY

PRINCIPLES AND MODERN APPLICATIONS

PETRUCCI HERRING MADURA BISSONNETTE

Slide 18 - 1 General Chemistry: Chapter 18 Copyright © 2017 Pearson Canada Inc.

Acid-Base Equilibria 18-1 Solubility Product Constant, Ksp

18-3 Common-Ion Effect in Solubility

18-4 Limitations of the Ksp Concept

18-6 Fractional Precipitation

Slide 18 - 2 General Chemistry: Chapter 18 Copyright © 2017 Pearson Canada Inc.

CaSO4(s) Ca2+(aq) + SO42−(aq)

Ksp = [Ca2+][SO42−] = 9.1×10−6 at 25°C

Slide 18 - 3 General Chemistry: Chapter 18 Copyright © 2017 Pearson Canada Inc.

g CaSO4/100 mL → mol CaSO4/L

The result is too large because conc was used instead of a

Slide 6 of 32 General Chemistry: Chapter 18 Copyright © 2011 Pearson Canada Inc.

Slide 7 of 32 General Chemistry: Chapter 18 Copyright © 2011 Pearson Canada Inc.

Slide 8 of 32 General Chemistry: Chapter 18 Copyright © 2011 Pearson Canada Inc.

Slide 9 of 32 General Chemistry: Chapter 18 Copyright © 2011 Pearson Canada Inc.

Slide 10 of 32 General Chemistry: Chapter 18 Copyright © 2011 Pearson Canada Inc.

Slide 11 of 32 General Chemistry: Chapter 18 Copyright © 2011 Pearson Canada Inc.

Slide 13 of 32 General Chemistry: Chapter 18 Copyright © 2011 Pearson Canada Inc.

Slide 14 of 32 General Chemistry: Chapter 18 Copyright © 2011 Pearson Canada Inc.

Slide 15 of 32 General Chemistry: Chapter 18 Copyright © 2011 Pearson Canada Inc.

Slide 16 of 32 General Chemistry: Chapter 18 Copyright © 2011 Pearson Canada Inc.

Slide 17 of 32 General Chemistry: Chapter 18 Copyright © 2011 Pearson Canada Inc.

Slide 18 of 32 General Chemistry: Chapter 18 Copyright © 2011 Pearson Canada Inc.

Slide 19 of 32 General Chemistry: Chapter 18 Copyright © 2011 Pearson Canada Inc.

The solubility of a slightly soluble ionic compound is lowered in the

Slide 18 - 25 General Chemistry: Chapter 18 Copyright © 2017 Pearson Canada Inc.

Slide 18 - 26 General Chemistry: Chapter 18 Copyright © 2017 Pearson Canada Inc.

The Diverse Noncommon Ion Effect: The Salt Effect

• Ionic interactions are important even when an ion is not apparently

Slide 18 - 27 General Chemistry: Chapter 18 Copyright © 2017 Pearson Canada Inc.

Slide 18 - 28 General Chemistry: Chapter 18 Copyright © 2017 Pearson Canada Inc.

Some ions join together in ion pairs.

Measured solubility of MgF2 is 4×10−3 M

Slide 18 - 29 General Chemistry: Chapter 18 Copyright © 2017 Pearson Canada Inc.

An ion pair, in a magnesium fluoride aqueous solution. The water molecules

Slide 18 - 30 General Chemistry: Chapter 18 Copyright © 2017 Pearson Canada Inc.

These must be taken into account if they affect the

Slide 18 - 31 General Chemistry: Chapter 18 Copyright © 2017 Pearson Canada Inc.

Slide 18 - 32 General Chemistry: Chapter 18 Copyright © 2017 Pearson Canada Inc.

Conflicting results are obtained as a result.

Useful predictions can still be made.

Slide 18 - 33 General Chemistry: Chapter 18 Copyright © 2017 Pearson Canada Inc.

AgI(s) Ag+(aq) + I−(aq)

Ksp = [Ag+][I−] = 8.5×10−17

Mix AgNO3(aq) and KI(aq) to obtain a solution

Q = [Ag+]init×[I−] init = (0.010)(0.015) = 1.5×10−4 > Ksp

Slide 18 - 34 General Chemistry: Chapter 18 Copyright © 2017 Pearson Canada Inc.

Qsp > Ksp Supersaturated, precipitation should occur.

Slide 18 - 35 General Chemistry: Chapter 18 Copyright © 2017 Pearson Canada Inc.

Slide 18 - 36 General Chemistry: Chapter 18 Copyright © 2017 Pearson Canada Inc.

Slide 18 - 37 General Chemistry: Chapter 18 Copyright © 2017 Pearson Canada Inc.

An aqueous solution that is 2.00 M in AgNO3 is slowly

Is separation of the two ions by selective precipitation

KspAgCl = 1.8 x 10-10, KspAgI = 8.5 x 10-17

Slide 38 of 38 General Chemistry: Chapter 17 Copyright © 2011 Pearson Canada Inc.

pH can affect the solubility of a salt.

Slide 18 - 43 General Chemistry: Chapter 18 Copyright © 2017 Pearson Canada Inc.

Mg(OH)2 (s) Mg2+(aq) + 2 OH−(aq) (18.2)

OH−(aq) + H3O+(aq) 2 H2O(l) (18.3)

Slide 18 - 44 General Chemistry: Chapter 18 Copyright © 2017 Pearson Canada Inc.

2 OH−(aq) + 2 H3O+(aq) 4 H2O(l) K' = (1/Kw)2 = 1.0×1028