Chemistry

Applications of
Aqueous Equilibria

Jill K. Robinson
John E. McMurry
Robert C. Fay

Copyright © 2020, 2016, 2012 Pearson Education, Inc. All Rights Reserved
Solubility Equilibria

• Many processes involve the dissolution or precipitation of slightly soluble compounds.

• Examples:
• Kidney stones: Ca2+(aq) + C2O42-(aq) ⇌ CaC2O4(s)
• Oxalate (C2O42-) is found in food and is typically excreted in urine.
• If it is not broken down (genetics), it can form kidney stones
(calcium oxalate, CaC2O4).

• Tooth decay: Ca5(PO4)3OH(s) ⇌ 5Ca2+(aq) + 3PO43-(aq) + OH-(aq)

• Tooth enamel consists primarily of hydroxyapatite, Ca5(PO4)3OH.
• Dissolves in the acids produced by bacteria decomposing foods rich in
sugar.
• How?

2
Copyright © 2020, 2016, 2012 Pearson Education, Inc. All Rights Reserved
 Solubility Equilibria VIDEO: Solubility Product Constant (Ksp)

• Molar solubility (S) is the maximum amount of solute that dissolves in enough water to make
one liter of solution.
• Solubility Product Constant (Ksp) is the equilibrium constant of all the ions of a slightly
soluble solid in solution.
• Describes a saturated solution of an ionic compound, or the equilibrium between the dissolved
(dissociated) ions and the undissolved solid.
• Calculated with concentrations of ions in a saturated solution.

n m y– x
Mm X x (s ) É mM n+
(aq ) + xX (aq )y–
K sp M X
At equilibrium, rate of dissolution = rate of precipitation

• A heterogeneous equilibrium exists between an

ionic solid and its ions in solution.
(dissolution)
Ex: CaF2(s) Ca2+(aq) + 2 F–(aq) Ksp = [Ca2+][F–]2
(precipitation) 3
Copyright © 2020, 2016, 2012 Pearson Education, Inc. All Rights Reserved
Solubility Equilibria
• Worked example 17.10:
Write the equilibrium-constant expression for the solubility product of silver chromate,
Ag2CrO4.

Answer: Ag2CrO4(s) ⇌ 2 Ag+(aq) + CrO42–(aq)

Ksp = [Ag+]2 [CrO42–]

4
Copyright © 2020, 2016, 2012 Pearson Education, Inc. All Rights Reserved
Measuring Ksp and Calculating Solubility from Ksp
Question: Calculate the equilibrium constant (Ksp) of a saturated solution of calcium fluoride
(CaF2) given [Ca2+] = 2.0 x 10-4 M and [F–] = 4.1 x 10-4 M.

CaF2 (s ) É Ca2+ (aq )+ 2F – (aq )

Answer:
Ksp = [Ca2+][F–]2

= (2.0 × 10–4) (4.1 × 10–4)2

= 3.4 × 10–11 (at 25ºC)

Temperature-dependent, just like all Kc’s

VIDEO: Introduction to solubility and solubility product constant

VIDEO: Solubility from the solubility

5
Copyright © 2020, 2016, 2012 Pearson Education, Inc. All Rights Reserved
Measuring Ksp and Calculating Solubility from Ksp
Table 17.3 Ksp Values for Some Ionic Compounds at 25°Celsius eText:
• Big Idea Question 17.5
Name Formula Ksp
• The value of Ksp indicates the solubility of an ionic
Aluminum hydroxide Al(OH)3 1.9 x 10-33
compound—the smaller the value, the less soluble
Barium carbonate BaCO3 2.6 x 10-9 the compound in water.
Calcium carbonate CaCO3 5.0 x 10-9 Ø However, in using Ksp values to compare
solubilities, you should choose compounds
Calcium fluoride CaF2 3.5 x 10-11 that have similar formulas (same cation-to-
Lead (II) chloride PbCl2 1.2 x 10-5 anion ratio), such as PbCrO4 and AgCl, or
CaF2 and PbCl2.
Lead (II) chromate PbCrO4 2.8 x 10-13
• Any combinations of concentrations equals
Silver chloride AgCl 1.8 x 10-10
the same Ksp at the same temperature.
Silver sulfate Ag2SO4 1.2 x 10-5
• Calculated values are only approximate.
• Different sources may have different values.
6
Copyright © 2020, 2016, 2012 Pearson Education, Inc. All Rights Reserved
 Measuring Ksp and Calculating Solubility from Ksp
Worked Example 17.12: Calculate the solubility of MgF2 in water at 25°C in (a) molarity and
(b) grams/liter. Ksp for MgF2 is 7.4 × 10–11.
MgF2 (s ) É Mg2+ (aq )+ 2F- (aq )
• Define x as the number of moles per
Answer: x 2x
liter of MgF2 that dissolves.
• Saturated solution contains x mol/L
of Mg2+ and 2x mol/L of F−.
• The molar solubility of the salt MgF2 is related to
the ion concentrations at equilibrium as follows:
[Mg2+] = x and [F–] = 2x • Since [Mg2+] = [MgF2] = x
a) x = Molar solubility of MgF2 = 2.6 x 10-4 M
Ksp = [Mg2+][F–]2
b) Expressed in g/L = 1.6 x 10-2 g/L
7.4 × 10–11 = (x) (2x)2

7.4 × 10–11 = 4x3 • When the problems are worked using this method,
the molar solubility will always be “x.”
x = 2.6 × 10–4 M = [Mg2+]
7
Copyright © 2020, 2016, 2012 Pearson Education, Inc. All Rights Reserved
Measuring Ksp and Calculating Solubility from Ksp
Question: The aqueous solubility of Lead (II) iodide in water at 25oC is 0.54 g/100 mL.
Calculate its Ksp at this temperature. (MM PBI2 = 461.0 g/mol)

Answer: PbI2(s) ⇌ Pb2+(aq) + 2I–(aq)

Ksp = [Pb2+][I–]2 x 2x

Since [Pb2+] = [PbI2] = x

Moles PbI2 = 0.54 g x 1 mol = 0.001171 mol [Pb2+] = x = 0.01171 M

461.0 g [I-] = 2x = 0.01171 x 2 = 0.02343 M

Ksp = [Pb2+][I–]2
x = Molar solubility = 0.001171 mol / 0.100 L
= 0.01171 M PbI2 = (0.01171)(0.02343)2

= 6.4 × 10–6
8
Copyright © 2020, 2016, 2012 Pearson Education, Inc. All Rights Reserved
 Factors That Affect Solubility VIDEO: Solubility and the common-ion effect

Solubility and the Common-Ion Effect

Worked Example 17.13: The molar solubility of MgF2 was calculated to be 2.6 x 10-4 M at 25℃
(Worked Example 17.12). What is the molar solubility of MgF2 in 0.10 M NaF at 25°C.
Ksp for MgF2 is 7.4 x 10-11.lsius
MgF2 (s ) É Mg2+ (aq )+ 2F- (aq )
Answer:
0 0.10
+x + 2x
x 0.10 + 2x
Ksp = [Mg2+][F–]2

7.4 × 10–11 = (x)(0.10 + 2x)2 x = [Mg2+] = Molar solubility MgF2

≈ (x)(0.10)2 = 7.4 × 10–9 M

• The calculated solubility of MgF2 in 0.10 M NaF is
–9
x = 7.4 × 10 M less than that in pure water.
9
Copyright © 2020, 2016, 2012 Pearson Education, Inc. All Rights Reserved
Factors That Affect Solubility VIDEO: The Common Ion Effect

Solubility and the Common-Ion Effect

MgF2 (s ) É Mg2+ (aq )+ 2F- (aq )

4
Molar solubility MgF2 : 2.6 10 M
Molar solubility of MgF2 in 0.10 M NaF : 7.4 10 9
M

Why does the solubility decrease in the presence of a common ion?

Le Châtelier’s Principle.

– Any factor that shifts equilibrium to the left (towards reactants) decreases solubility.
– Any factor that shifts equilibrium to the right (towards products) increases solubility.

10
Copyright © 2020, 2016, 2012 Pearson Education, Inc. All Rights Reserved
Factors That Affect Solubility
Solubility and the Common-Ion Effect

MgF2 (s ) É Mg2+ (aq )+ 2 F- (aq )

11
Copyright © 2020, 2016, 2012 Pearson Education, Inc. All Rights Reserved
Solubility and the Common-Ion Effect
Question: Taking Ksp of BaSO4 to be 1.1 x 10-10, estimate its solubility (moles per liter) in 0.10 M
Na2SO4 solution.

a) 1.1 x 10-9 M Answer:

b) 1.0 x 10-5 M Na2SO4 – strong electrolyte – complete dissociation
c) 1.1 x 10-11 M
d) 1.1 x 10-10 M Na2SO4 (s) → 2Na+(aq) + SO42–(aq)
0.10 M 0.20 M 0.10 M

BaSO4(s) ⇌ Ba2+(aq) + SO42–(aq)

Ksp = [Ba2+][SO42–]2
0 0.10 1.1 x 10-10 = (x)(0.10 + x)
+x +x ≈ (x)(0.10)
x 0.10 + x x = 1.1 x 10-9 M

x = [Ba2+] = Molar solubility BaSO4

= 1.1 x 10-9 M
Copyright © 2020, 2016, 2012 Pearson Education, Inc. All Rights Reserved
 Factors That Affect Solubility VIDEO: Solubility and the pH of the solution

Solubility and the pH of the Solution

CaCO3(s) ⇌ Ca2+(aq) + CO32–(aq) Regular dissolution reaction (in pure water)

But if we add acid, this happens: CO32-(aq) + H3O+(aq) ⇌ HCO3–(aq) + H2O(l)

• The basic anion (CO32-) is a strong conjugate base of a weak acid.

• CO32− combine with protons to give bicarbonate ions (HCO3−)

• [CO32-] decreases, and the solubility equilibrium of CaCO3 shifts to the right.
CaCO3 (s) ⇌ Ca2+(aq) + CO32-(aq)
• Solubility of calcium carbonate increases as pH decreases.
• Solubility of an ionic compound with a basic anion (from a weak acid) increases as pH decreases.
13 Copyright © 2020, 2016, 2012 Pearson Education, Inc. All Rights Reserved
 Factors That Affect Solubility
Solubility and the pH of the Solution

• Solubility of an ionic compound with a basic anion (from a

weak acid) increases as pH decreases.

Fig. 17.13 Plot of solubility of CaCO3 at 25℃ vs pH of the solution.

• Other salts that contain basic anions (from weak acids), such as CO32- , CN-, PO43-, S2-, F-,
behave similarly. Why? Remember: Weak acids have strong conjugate bases capable of being
protonated

• pH has no effect on salts with anions of strong acids, such as Cl-, Br-, I-, NO3-, and ClO4-.
Why? Remember: Strong acids have weak conjugate bases that are not capable
of being protonated
14 Copyright © 2020, 2016, 2012 Pearson Education, Inc. All Rights Reserved
Factors That Affect Solubility
Solubility and the pH of the Solution

• Question: What happens to the solubility of calcium fluoride with the addition of a weak acid?

1) Regular Dissolution Reaction: CaF2(s) ⇌ Ca2+(aq) + 2F-(aq)

Add weak acid:
Basic Anion
HA(aq) + H2O(l) ⇌ H3O+(aq) + A-(aq)
acid
2) Rxn of basic anion with the acid: 2H3O (aq) + 2F (aq) ⇌ 2HF(aq) + 2H2O(l)
+ -

Net ionic equation: CaF2(s) + 2H3O+(aq) ⇌ Ca2+(aq) + 2HF(aq) + 2H2O(l)

• With the addition of a weak acid, F− combine with protons to give HF

• [F-] decreases, and the solubility equilibrium of CaF2 shifts to the right.

• Solubility of calcium fluoride increases with the addition of a weak acid (as pH decreases).
15
Copyright © 2020, 2016, 2012 Pearson Education, Inc. All Rights Reserved
 Factors That Affect Solubility
Solubility and the pH of the Solution
• Question 17.113 Which of the following compounds are more soluble in an acidic solution than in
pure water? Write a balanced net ionic equation for each dissolution reaction.
a. AgBr
b. CaCO3
c. Ni(OH)2
d. Ca3(PO4)2
Answer: (b), (c) and (d) are more soluble in acidic solution. (As the basic anions of weak acids are
protonated, the solubility equilibrium of the salts shifts to the right, increasing the solubility).
b. CaCO3(s) ⇌ Ca2+(aq) + CO32-(aq)
a. AgBr(s) ⇌ Ag (aq) + Br (aq)
+ -

Add H3O+(aq) Add H3O+(aq)

H3O+(aq) + CO32-(aq) ⇌ HCO3-(aq) + H2O(l)
HBr is a strong acid
Br- is not protonated Net ionic equation:
No change CaCO3(s) + H3O+(aq) ⇌ Ca2+(aq) + HCO3-(aq) + H2O(l)
16 Copyright © 2020, 2016, 2012 Pearson Education, Inc. All Rights Reserved
 Factors That Affect Solubility
Solubility and the pH of the Solution
• Question 17.113 Which of the following compounds are more soluble in an acidic solution than in
pure water? Write a balanced net ionic equation for each dissolution reaction.
a. AgBr
b. CaCO3
c. Ni(OH)2
d. Ca3(PO4)2

c. Ni(OH)2(s) ⇌ Ni2+(aq) + 2OH-(aq) d. Ca3(PO4)2(s) ⇌ 3Ca2+(aq) + 2PO43-(aq)

Add H3O+(aq) Add H3O+(aq)

2H3O+(aq) + 2OH- (aq) ⇌ 4H2O(l) 2H3O+(aq) + 2PO43- (aq) ⇌ 2HPO42-(aq) + 2H2O(l)

Net ionic equation: Net ionic equation:

Ni(OH)2(s) + 2H3O+(aq) ⇌ Ni2+(aq) + 4H2O(l) Ca3(PO4)2(s)+ 2H3O+(aq) ⇌ 3Ca2+(aq) + 2HPO42-(aq) + 2H2O(l)

Copyright © 2020, 2016, 2012 Pearson Education, Inc. All Rights Reserved
Precipitation of Ionic Compounds VIDEO: Predicting Precipitation
With Ksp Values
• Application: Separating mixtures based on solubility.

• Example: If solutions of CaCl2 and NaF are combined, will a precipitate of CaF2 form?

CaF2 (s ) É Ca2+ (aq )+ 2 F- (aq )

• Use solubility guidelines (Section 4.6:Table 4.2 - Solubility Guidelines for Ionic Compounds in
Water) and the Ion-Product (IP).

• Ion-Product (IP): Solubility product constant for a solid substance in an aqueous solution not
necessarily at equilibrium (is to Ksp what Qc is to Kc ).

2 2
K sp Ca F

2 2
Q
IPc Ca F Note: t = some point in time where
t t
rxn is not necessarily at equilibrium
18
Copyright © 2020, 2016, 2012 Pearson Education, Inc. All Rights Reserved
Precipitation of Ionic Compounds
Table 4.2 Solubility Guidelines for Ionic Compounds in Water

19
Copyright © 2020, 2016, 2012 Pearson Education, Inc. All Rights Reserved
Precipitation of Ionic Compounds

Compare the IP to Ksp

• If IP > Ksp: solution is supersaturated, and precipitation will occur.

• If IP = Ksp: solution is saturated, and equilibrium exists already.

• If IP < Ksp: solution is unsaturated, and precipitation will not occur.

20
Copyright © 2020, 2016, 2012 Pearson Education, Inc. All Rights Reserved
Precipitation of Ionic Compounds
• Question: If equal volumes of aqueous 0.50 M CaCl2 and 0.50 M NaF are mixed, will a
precipitate of CaF2 form? Ksp for CaF2 = 3.5 x 10-11
CaCl2(aq) + 2NaF(aq) à CaF2(?) + 2NaCl(aq)

CaF2 (s ) É Ca2+ (aq )+ 2 F- (aq )

Answer: Ksp = [Ca2+][F-]2 = 3.5 × 10–11
On mixing equal volumes of two solutions, the concentrations of both
solutions are cut in half ([Ca2+]t = 0.25 M; [F-]t = 0.25 M)

IP = [Ca2+]t [F-]2t
= (0.25)(0.25)2
IP = 0.016
IP > Ksp
The solution will be supersaturated - CaF2 will precipitate.
Copyright © 2020, 2016, 2012 Pearson Education, Inc. All Rights Reserved
 Precipitation of Ionic Compounds
• Worked Example 17.16: Will a precipitate form when 0.150 L of 0.10 M Pb(NO3)2 and 0.100 L of
0.20 M NaCl are mixed? Use Appendix C for Ksp values.
Answer: We need to find the concentration of Pb2+ and Cl-
in the final solution (Vf = 0.250 L)
• Pb(NO3)2(aq) + NaCl(aq) à PbCl2(?) or NaNO3 (?)
mol = Conc x vol
• Ionic compounds are strong electrolytes and
mol Pb2+ = 0.10 M x 0.150 L = 0.015 mol
dissociate in solution.
mol Cl- = 0.20 M x 0.100 L = 0.020 mol
– Pb(NO3)2(aq) à Pb2+(aq) + 2NO3(aq) Vf = Total volume = 0.150 L + 0.100 L = 0.250 L
– NaCl(aq) à Na+(aq) + Cl-(aq) [Pb2+]F = 0.015 mol / 0.250 L = 0.060 M
• Precipitation: PbCl2 or NaNO3? [Cl-]F = 0.020 mol / 0.250 L = 0.080 M
• Use Table 4.2 to find the insoluble product: Or we can use Ci x Vi = Cf x Vf to find their concentrations
PbCl2(s) might precipitate (insoluble) in the final solution (Vf = 0.250 L):
[Pb2+]i x Vi = [Pb2+]F x VF
PbCl2(s) ⇌ Pb2+(aq) + 2Cl-(aq) 0.10 M x 0.150 L = [Pb2+]F x 0.250 L [Pb2+]F = 0.060 M
Ksp = 1.2 x 10-5 [Cl-]i x Vi = [Cl-]F x VF
0.20 M x 0.100 L = [Cl-]F x 0.250 L [Cl-]F = 0.080 M
Copyright © 2020, 2016, 2012 Pearson Education, Inc. All Rights Reserved
 Precipitation of Ionic Compounds
• Worked Example 17.16: Will a precipitate form when 0.150 L of 0.10 M Pb(NO3)2 and 0.100 L of
0.20 M NaCl are mixed? Use Appendix C for Ksp values.
Answer:
Final solution (V = 0.250 L):
[Pb2+]F = 0.060 M
PbCl2(s) ⇌ Pb2+(aq) + 2Cl-(aq)
[Cl-]F = 0.080 M
Ksp = 1.2 x 10-5

IP = [Pb2+]t [Cl–]2t
=(0.060) (0.080)2
= 3.8 x 10-4 > Ksp

IP is greater than Ksp: PbCl2 will precipitate.

Copyright © 2020, 2016, 2012 Pearson Education, Inc. All Rights Reserved
Measuring Ksp and Calculating Solubility from Ksp

VIDEO: Ksp - Molar Solubility, Ice Tables, & Common Ion Effect

VIDEO: Example: Determining Whether a Precipitate Will Form

(Solubility Equilibrium #3)

Copyright © 2020, 2016, 2012 Pearson Education, Inc. All Rights Reserved