Ksp and Solubility

Ksp and Solubility

Introduction to Solubility Equilibria

Calculating Ksp from Solubility

Calculating Solubility from Ksp

Factors Affecting Solubility

 Precipitation

AP Style Problems

Introduction to Solubility
Equilibria
 Introduction to Solubility Equilibria

Many shells are made of relatively insoluble calcium carbonate, so the

shells are not at huge risk of dissolving in the ocean.

There are several ionic compounds that are insoluble or sparingly

soluble in water like calcium carbonate.
 Introduction to Solubility Equilibria

The study of solubility equilibria pertains to insoluble ionic

compounds (salts).
If a salt is soluble, it dissolves completely; there is no
equilibrium.
Even an insoluble salt will dissociate in water to a small degree,
until it reaches equilibrium.
The equilibrium will be between the undissolved solid and the
ions which dissociated into the solution.
Determining that equilibrium is the focus of this unit.
 Introduction to Solubility Equilibria
Ionic compounds dissociate into their ions to different degrees when
placed in water.
The ions reach equilibrium with the non-dissociated solid phase and
the solution is now saturated.
When a small amount of CaCO3(s) is added to water, the following
equilibrium is established:

CaCO3(s) ↔ Ca (aq) + CO3 (aq)

2+ 2-

A saturated solution of CaCO3(s)

2+ 2-
Ca CO3

CaCO3(s)
 Introduction to Solubility Equilibria

Na2CO3 is a soluble ionic

salt, so there is no
precipitate in the solution.

CaCO3 is a relatively
insoluble ionic salt.
 Introduction to Solubility Equilibria
Consider the equilibrium that exists in a saturated solution of
CaCO3 in water:
CaCO3(s) ↔ Ca (aq) + CO3 (aq)
2+ 2-

Unlike acid-base equilibria which are

homogenous, solubility equilibria are
heterogeneous, there is always a solid
in the reaction.

Since the solubility of calcium

carbonate is negligible, very few ions
are present in the solution as opposed
to the undissociated calcium
carbonate solid.
 Introduction to Solubility Equilibria
CaCO3(s) ↔ Ca (aq) + CO3 (aq)
2+ 2-

The small amount of the ions formed from the dissociation are
always in equilibrium with the undissolved solid.

The equilibrium constant, Ksp for this equilibrium reaction is:

2+ 2−
Ksp = [Ca ] [CO3 ]
Ksp is also called the solubility product constant or solubility
product.

There is never any denominator in Ksp expressions because pure

solids are not included in any equilibrium expressions.
 Solubility Equilibrium
The degree to which an ionic compound dissociates in water is
indicated by its Ksp.
2+ 2- 0 -9
CaCO3(s) ↔ Ca (aq) + CO3 (aq) Ksp 25 C = 5.0 x 10
2+ 2- 0 -6
MgCO3(s) ↔ Mg (aq) + CO3 (aq) Ksp 25 C = 6.8 x 10

In both saturated solutions, the equilibrium lies far to the left,

meaning relatively few aqueous ions are present in solution.

MgCO3 has a higher Ksp value, which means that it has a higher
solubility.

A higher Ksp value indicates there will be more ions in solution at

equilibrium.
 Example 1: Solubility Equilibrium
Write the dissociaton equation and provide the solubility product
constant expression for the salt MgF2.
 Example 1: Solubility Equilibrium
Write the dissociaton equation and provide the solubility product
constant expression for the salt MgF2.

The dissociation equation is:

MgF2(s) ↔ Mg (aq) + 2 F (aq)
2+ -

and
2+ - 2
Ksp = [Mg ] [F ]
 Solubility
The term solubility represents the maximum amount of solute that
can be dissolved in a certain volume before any precipitate is
observed.

The solubility of a substance can be given in terms of grams per

liter(g/L) or moles per liter(mol/L).

When solubility is given in mol/L it is referred to as molar solubility.

Molar solubility indicates the number of moles of the compound that

will be dissolved in one liter of a saturated solution.

The molar solubility does not necessarily reflect the concentration of

a particular ion in that solution.
 Example 2: Solubility
What is the maximum number of grams of BaC2O4 that will
dissolve in 2.5 L before a precipitate occurs? The solubility of
-3
BaC2O4 is 1.3 x 10 mol/L.
 Example 2: Solubility
What is the maximum number of grams of BaC2O4 that will
dissolve in 2.5 L before a precipitate occurs? The solubility of
-3
BaC2O4 is 1.3 x 10 mol/L.

The dissociation equation for barium oxalate, BaC2O4 is

2+ 2-
BaC2O4 (s) ↔ Ba (aq) + C2O4 (aq)
From the above equation, we determine the ratio of cations to
anions is 1:1.
-3 2+
This means that 1.3 x 10 moles of Ba can dissolve in 1 L.

0.73 g is the maximum amount of BaC2O4 that will dissolve

in 2.5 L before a precipitate forms.
 Example 3: Solubility
Consider the slightly soluble compound lead (II) chloride, PbCl2,
2+ -
with a solubility of 0.016 mol/L. How many moles of Pb and Cl
will be present when one mole of PbCl2 is placed in 1 L of water?
 Example 3: Solubility
Consider the slightly soluble compound lead (II) chloride, PbCl2,
2+ -
with a solubility of 0.016 mol/L. How many moles of Pb and Cl
will be present when one mole of PbCl2 is placed in 1 L of water?

PbCl2(s) ↔ Pb (aq) + 2Cl (aq)

2+ -

The ratio of cations to anions is 1:2.

2+
Therefore, 0.016 mol of Pb will be present in 1 L of water.
-
Twice as much, or 2(0.016 mol) = 0.032 mol of Cl will be present in
1 L of water.
 Example 4: Solubility
Consider the slightly soluble compound, silver sulfate, Ag2SO4, with a
+ 2-
solubility of 0.015 mol/L. How many moles of Ag and SO4 will be
present when one mole of Ag2SO4 is placed in 1 L of water?
 Example 4: Solubility
Consider the slightly soluble compound, silver sulfate, Ag2SO4, with a
+ 2-
solubility of 0.015 mol/L. How many moles of Ag and SO4 will will be
present when one mole of Ag2SO4 is placed in 1 L of water?
Ag2SO4 (s) ↔ 2 Ag (aq) + SO4 (aq)
+ 2-

The ratio of cations to anions is 2:1.

2-
Therefore, 0.015 mol of SO4 will be present in 1 L of water.
+
Twice as much, or 2(0.015 mol) = 0.030 mol of Ag will be present in
1 L of water.
 Molar Solubility
The molar solubility of an ionic salt is the molar equivalent (mol/L) of
the solid that has dissociated into its ions.
It can be determined by either:

Measuring the concentration of ions in solution directly.

Using the equilibrium constant to first calculate the concentration of

ions and then use this to find the molar solubility.

When solubility is given in mol/L it is referred to as molar solubility.

 Example 5: Molar Solubility
+ -8
Given a saturated silver carbonate solution where [Ag ] = 2.4 x 10 M.
a) What is the molar solubility of the Ag2CO3?
b) How would you determine how many grams of silver carbonate are
dissolved in the solution?
 Example 5: Molar Solubility
+ -8
Given a saturated silver carbonate solution where [Ag ] = 2.4 x 10
mols per Liter?
a) What is the molar solubility of the Ag2CO3?
Calculate the molar solubility from ion concentrations by using
stoichiometrical ratios.
+ 2-
Ag2CO3(s) ↔ 2Ag (aq) + CO3 (aq)
For every 2 silver ions in solution, 1 Ag2CO3 is required to
dissociate. Given 1L of the solution;

Molar solubility of Ag2CO3

 Example 5: Molar Solubility
+ -8
Given a saturated silver carbonate solution where [Ag ] = 2.4 x 10
mols per Liter?
b) How would you determine how many grams of silver carbonate are
dissolved in the solution?
+ 2-
Ag2CO3(s) ↔ 2Ag (aq) + CO3 (aq)

Convert to grams by multiplying the moles of silver carbonate

with the molar mass of Ag2CO3.
 Example 6: Molar Solubility
What is the molar solubility of a saturated aqueous solution of PbI2?
-8 o
Ksp = 1.39 x 10 25 C
 Example 6: Molar Solubility
What is the molar solubility of a saturated aqueous solution of PbI2?
-8 o
Ksp = 1.39 x 10 @ 25 C
Write the equilibrium expression.
2+ -
PbI2(s) ↔ Pb (aq) + 2 I (aq)
2+
For every 1 Pb produced there
-
will be 2 I produced.

2+
[Pb ] [I ]
- The equilibrium expression
shows that 1 mol PbI2 produces
Initial 0 0 2+
1 mol of Pb , so the molar
2+
Change +x +2x solubility of PbI2(s) = [Pb ] =
-3
1.51 x 10 M.
Equilibrium x 2x
 Solubility
Molar solubility refers to the ion with the lower mole ratio. It does
not always refer to the cation, although in many cases it does.

Molar solubility of
[Cation] [Anion
compound the compound
mol/L mol/L]
mol/L
-3 -3 -3
BaC2O4 1.3 x 10 1.3 x 10 1.3 x 10
PbCl2 0.016 0.016 0.032
Ag2SO4 0.015 0.030 0.015

In BaC2O4 the molar solubility is the same as that of the cation or

anion since the cation:anion ratio is 1:1.
In PbCl2, the molar solubility is the same as that of the cation and
one half of the anion since the cation: anion ratio is 1:2.
In Ag2SO4, the molar solubility is the same as that of the anion
and one half of the cation since cation : anion ratio is 2:1.
1 Which Ksp expression is correct for AgCl?
+ -
A [Ag ]/[Cl ]
+ -
B [Ag ][Cl ]
2+ 2 2- 2
C [Ag ] [Cl ]
D None of the above
E I need help

B
2 Given the reaction at equilibrium:
2+ -
Zn(OH)2(s) Zn (aq) + 2 OH (aq),
what is the expression for the solubility product
constant, Ksp, for this reaction?
2+ - 2
A Ksp= [Zn ][OH ] / [Zn(OH)2]
2+ -
B Ksp= [Zn(OH)2] / [Zn ][2 OH ]
2+ -
C Ksp= [Zn ][2 OH ]
2+ - 2
D Ksp= [Zn ][OH ]
E I need help
D
3 Which Ksp expression is correct for Fe3(PO4)2?
2+ 3 3- 2
A [Fe ] [PO4 ]
2+ 3 3- 2
B [Fe ] /[PO4 ]
3+ 2 3- 2
C [Fe ] [PO4 ]
D None of the above
E I need help

A
4 When 30 grams of NaCl are mixed into 100 mL of distilled
water all of the solid NaCl dissolves. The solution must be
saturated and the Ksp for the NaCl must be very high.

A True

B False

C I need help

B
 -5
5 If the solubility of barium carbonate, BaCO3 is 7.1 x 10 M,
2+
this means that a maximum of _____ Ba ions can be
dissolved per liter of solution.

A -5
7.1 x 10 moles
-5
B 3.5 x 10 moles
-4
C 1.4 x 10 moles
-5
D 1.8 x 10 moles
E I need help

A
 -5
The solubility of Ag2CrO4 is 6.5 x 10 M. This means that
+
a maximum of _____silver ions, Ag , can be dissolved
per liter of solution.
-5
A 6.5 x 10 moles
-5
B twice 6.5 x 10 moles
-5
C half 6.5 x 10 moles
-5
D one-fourth 6.5 x 10 moles
E I need help

B
Calculating Ksp from
Solubility
 Calculating Ksp from the Solubilty
When molar solubility is known, the equilibrium concentrations of
the ions can be determined from the solubility and the ratios
discussed in the previous topic.

These values are then placed into the Ksp expression and the value
for the Ksp is calculated.
 Example 1: Calculating Ksp
-2
The molar solubility of lead (II) bromide, PbBr2 is 1.0 x 10 mol/L at
o
25 C. Calculate the solubility product, Ksp, for this compound.
 Example 1: Calculating Ksp
-2
The molar solubility of lead (II) bromide, PbBr2 is 1.0 x 10 mol/L at
o
25 C. Calculate the solubility product, Ksp, for this compound.
PbBr2(s) ↔Pb (aq) + 2 Br (aq)
2+ -

The molar solubility refers to the ion with the lower molar ratio,
2+ -2
[Pb ] = 1.0 x 10 mol/L
- -2 -
[Br ] = 2 x 1.0 x 10 mol/L, since 1 PbBr2 produces 2 Br ions

Substitute the molar concentrations into the Ksp expression and

solve.
 Example 2: Calculating Ksp
Given a saturated solution of Fe(OH)3 with a pH of 11.3.
a) What is the Ksp of the solution?
b) If an acid was added and reacted with some of the hydroxide ion,
would the Ksp increase, decrease, or remain the same?
 Example 2: Calculating Ksp
Given a saturated solution of Fe(OH)3 with a pH of 11.3.
a) What is the Ksp of the solution?

-
Write the equilibrium expression, find [OH ] using the pOH equation
3+
and then find [Fe ] using the mole ratio.
3+ -
Fe(OH)3(s) ↔ Fe (aq) + 3 OH (aq)
3+ - 3
Ksp = [Fe ][OH ]
3+ -
The equilibrium equation indicates that [Fe ] = 1/3 [OH ]
 Example 2: Calculating Ksp
Given a saturated solution of Fe(OH)3 with a pH of 11.3.
b) If an acid was added and reacted with some of the hydroxide ion,
would the Ksp increase, decrease, or remain the same?

3+ -
Fe(OH)3(s) ↔ Fe (aq) + 3 OH (aq)

The Ksp remains the same.

- +
When an acid is added, the OH ions are neutralized by the H ions
-
and the [OH ] decreases.
3+
The [Fe ] would increase according to Le Chatliers principle as
more solid dissociates shifting the equilibrium to the right to
-
compensate for the loss of OH ions.
As long as the solution remains saturated, the Ksp value remains
the same.
7 For the slightly soluble salt, CoS, the molar solubility is
-5
5 x 10 M. Calculate the Ksp for this compound.

-5
A 5 x 10
-4
B 1.0 x 10
-10
C 5 x 10
-9
D 2.5 x 10
E I need help D
8 For the slightly soluble salt, BaF2, the molar solubility
-4
is 3 x 10 M. Calculate the solubility-product constant
for this compound.

-4
A 9 x 10
-8
B 9 x 10
-7
C 1.8 x 10
-10
D 1.08 x 10
D
E I need help
9 For the slightly soluble salt, La(IO3)3, the molar
-4
solubility is 1 x 10 M. Calculate Ksp.

-12
A 3 x 10
-16
B 3 x 10
-11
C 2.7 x 10

D 2.7 x 10-15 D

E I need help
10 For the slightly soluble compound, Ca3(PO4)2, the
-8
molar solubility is 3 x 10 moles per liter. Calculate
the Ksp for this compound.

A 9.00 x 10 -16
-38
B 1.08 x 10
-36
C 2.62 x 10
-13
D 1.35 x 10
E I need help C
11 The concentration of hydroxide ions in a saturated
-15
solution of Al(OH)3 is 1.58 x 10 . What is the Ksp of
Al(OH)3?

A 2.50 x 10-30
B 1.49 x 10-46
C 2.81 x 10-31
D 2.10 x 10-60
E I need help
D
12 What is the Ksp of Fe(OH)3(s) if a saturated solution of it
has a pH of 11.3?
-12
A 2.0 x 10

B 5.4 x 10-12
-46
C 2.1 x 10
-15
D 1.6 x 10
E I need help
B
Calculating Solubility
from Ksp
 Calculating Solubilty from the Ksp

where x is the solubility. Many texts use "s" in place of "x"

Example 1: Calculating Solubility from Ksp
What is the molar solubility of a saturated aqueous solution of
-9
BaCO3? Ksp = 5.0 x 10 .
Example 1: Calculating Solubility from Ksp
What is the molar solubility of a saturated aqueous solution of
-9
BaCO3? Ksp = 5.0 x 10 .

Write the equilibrium equation:

2+ 2-
BaCO3(s) ↔ Ba (aq) + CO3 (aq)

2+ 2-
The equation indicates a 1:1 ratio of Ba and CO3 ions in the
solution. The molarity of one of the ions = the molar solubility of
BaCO3(s).
Example 1: Calculating Solubility from Ksp
What is the molar solubility of a saturated aqueous solution of
-9
BaCO3? Ksp = 5.0 x 10 .
2+ 2-
BaCO3(s) ↔ Ba (aq) + CO3
(aq)
2+ 2-
[Ba ] [CO3 ]

Initial 0 0
Change +x +x

Equilibrium x x

2+ 2- -5
x = [Ba ] = [CO3 ] = 7.07 x 10 M
2+ 2-
Since 1 Ba or 1 CO3 are required for 1 BaCO3, the molar
-5
solubility of the BaCO3(s) = 7.07 x 10 M.
Example 2: Calculating Solubility from Ksp
What is the molar solubility of a saturated aqueous solution of PbI2?
-8
Ksp = 1.39 x 10 .
Example 2: Calculating Solubility from Ksp
What is the molar solubility of a saturated aqueous solution of PbI2?
-8
Ksp = 1.39 x 10 .

Write the equilibrium equation:

PbI2(s) ↔ Pb (aq) + 2I (aq)
2+ -

2+ -
The equation indicates a 1:2 ratio of ions Pb and I ions in the
2+
solution. The molarity of the Pb ion = the molarity of PbI2.
Example 2: Calculating Solubility from Ksp
What is the molar solubility of a saturated aqueous solution of PbI2?
-8
Ksp = 1.39 x 10 .
Since neither ion concentration is
PbI2(s) ↔ Pb (aq) + 2I (aq)
2+ -
2+
known, substitute x for [Pb ] and
-
2x for [I ].
2+ -
[Pb ] [I ]

Initial 0 0
Change +x +2x

Equilibrium x 2x

2+
Since 1 Pb formed from 1 PbI2, the molar
-3
solubility of the PbI2(s) = 1.51 x 10 M.
13 Calculate the concentration of silver ion when the
-16
solubility product constant of AgI is 1 x 10 .

-16
A 0.5 x 10
-16
B 2 x 10
-32
C 1 x 10
-8
D 1 x 10
E I need help

D
14 Calculate the molar solubility of PbF2 that has a Ksp at
-6
25℃ = 3.6 x 10 .

-3
A 1.9 x 10
-3
B 9.7 x 10
-6
C 1.8 x 10
-6
D 9.7 x 10
E I need help
B
 -18.
15 The Ksp of a compound of formula AB3 is 1.8 x 10
What is the molar solubility of the compound?
-5
A 1.6 x 10
-6
B 1.2 x 10
-9
C 1.3 x 10
-19
D 4.5 x 10
E I need help

A
 -18.
16 The Ksp of a compound of formula AB3 is 1.8 x 10
The molar mass is 280g/mol. What is the solubility?
-3
A 4.5 x 10 g/L
-5
B 1.5 x 10 g/L
-7
C 3.8 x 10 g/L
-9
D 1.3 x 10 g/L
E I need help

A
17 Which of the following ionic salts has the highest molar
solubility?

A NiCO3(s) Ksp = 6.61 x 10-9

B MnCO3(s) Ksp = 1.82 x 10-11

C ZnCO3(s) Ksp = 1.45 x 10-11

D Ag2CrO4(s) Ksp = 9.00 x 10-12

E I need help
D
Factors Affecting Solubility
 Common Ion Effect

Consider a saturated solution of barium sulfate:

2+ 2-
BaSO4(s) ↔ Ba (aq) + SO4 (aq)

Adding one of the above ions to this solution would shift the
equilibrium to the BaSO4(s) and the solubility of the salt will
decrease.
2+ 2-
So adding any soluble salt containing either Ba or SO4 ions will
decrease the solubility of barium sulfate.
 Example 1: Common Ion Effect
Calculate the solubility of CaF2 in grams per liter in:
a) pure water
b) a 0.15 M KF solution
c) a 0.080 M Ca(NO3)2 solution
-11
The solubility product for calcium fluoride, CaF2 is 3.9 x 10
 Example 1: Common Ion Effect
a) Calculate the solubility of CaF2 in grams per liter in pure water

2+ -
CaF2(s) ↔ Ca (aq) + 2 F (aq)

2+ -
[Ca ] [F ]

Initial 0 0
Change +x +2x

Equilibrium x 2x
 Example 1: Common Ion Effect
b) Calculate the solubility of CaF2 in grams per liter in a 0.15 M KF
solution
KF is a strong electrolyte and is completely dissociated and serves
- -
as the major source of F ions. [F ] =0.15 M
-11
The solubility product for calcium fluoride, CaF2 is 3.9 x 10
- -
[ F ] = 0.15 M; this represents the total amount of F ions present in
the solution and will be substituted in the Ksp equation.

-7
Solubility of CaF2 in 0.15 M KF is = 1.35 x 10 grams/L
 Example 1: Common Ion Effect
c) Calculate the solubility of CaF2 in grams per liter in a 0.080 M
Ca(NO3)2 solution.
2+ -
CaF2(s) ↔ Ca (aq)+2 F (aq)

Ca(NO3)2 is a strong electrolyte and is completely dissociated and

2+ 2+
serves as the major source of Ca ions. [Ca ] =0.080 M
-11
The solubility product for calcium fluoride, CaF2 is 3.9 x 10 .
2+ 2+
[Ca ] =0.080 M; this represents the total amount of Ca ions
present in the solution and is substituted in the Ksp equation.
-
For each mole of CaF2 , two moles of F is formed.
-
Solubility of CaF2 is 1/2 the amount of of F .
 Example 1: Common Ion Effect
c) Calculate the solubility of CaF2 in grams per liter in a 0.080 M Ca(NO3)2
solution.
2+ -
CaF2(s) ↔ Ca (aq)+2 F (aq)

2+ -
[Ca ] [F ]

Initial 0.080 0
Change +x +2x

Equilibrium 0.080+x 2x

-
Solubility of CaF2 in 0.080 M Ca(NO3)2 equals half the amount of F ions
-
since only 1 mol of CaF2 is required to produce 2 moles of F ions.
 Common Ion Effect
The Common-Ion Effect states that adding a soluble salt
containing common ions to an insoluble salt solution will decrease
the solubility of the sparingly soluble salt.

Compare the solubilities from the previous example:

2+ -
CaF2(s)↔ Ca (aq)+2 F (aq)

Solubility of CaF2
CaF2 dissolved with:
(g/L)
pure water 0.016
-7
0.015 M KF 1.35 x 10
-4
0.080 M Ca(NO3)2 8.6 x 10
These results support Le Chatelier's Principle: Increasing the
concentration of one of the common ions on the product side shifts
the equilibrium to the reactant. Solubility decreases compared to
that of pure water.
 Changes in pH
The solubility of almost any ionic compound is affected by changes
in pH.
Consider the dissociation equation for magnesium hydroxide:

Mg(OH)2(s) ↔ Mg (aq) + 2 OH (aq)

2+ -

-
When the pH is lowered the solution becomes acidic. The OH ions
present in the solution are neutralized by the added acid.
-
The [OH ] decreases.
-
To compensate for the loss of [OH ], more solid dissolves into the
solution, shifting the equilibrium to the right.

As a result the solubility increases.

 Changes in pH
Consider the dissociation of the salt calcium fluoride:
CaF2 (s) ↔ Ca (aq)+2 F (aq)
2+ -
-
When the pH is lowered by adding acid, the F ions interact with
+
the H ions to form HF.
-
F is the conjugate base of a weak acid, HF.
- + -
As F interacts with the added H ions from the acid, [F ]
decreases.
-
The equilibrium will shift to the products, producing more F ions
2+
and Ca ions, increasing the solubility of CaF2 .
 Changes in pH
If a substance has a basic anion, it will be more soluble in an
acidic solution.
If a substance has an acidic cation, it will be more soluble in
basic solutions.

.
18 What is the molar solubility of a saturated solution of
-12
Ag2CrO4? Ksp at 25℃ is = 1.2 x 10 .

-4
A 1.1 x 10

B 6.7 x 10-5
-5
C 8.4 x 10
-7
D 5.5 x 10
E I need help B
19 What is the molar solubility of a saturated solution of
-12
Ag2CrO4 in 0.100 M K2CrO4? Ksp at 25℃ is = 1.2 x 10 .

-12
A 3.0 x 10

B 6.3 x 10-5
-8
C 5.1 x 10
-6
D 1.7 x 10

E I need help D
20 What is the molar solubility of a saturated solution of
-12
Ag2CrO4 in 0.200 M AgCl? Ksp at 25℃ is = 1.2 x 10 .

-11
A 3.0 x 10

B 6.3 x 10-5
-11
C 3.11 x 10
-7
D 3.5 x 10 A
E I need help
21 Given the system at equilibrium
+ -
AgCl(s) Ag (aq) + Cl (aq)

When 0.01M HCl is added to the sytem, the equilibrium

will shift to the ________.

+
A products and the concentration of Ag will decrese
+
B Products and the concentration of Ag will increase
+
C Reactant and the concentration of Ag will decrease
+
D Reactant and the concentration of Ag will increase
E I need help
C
22 Which of the following substances are more soluble in
acidic solution than in basic solution?

A PbCl2
B Ba(NO3)2
C AgI
D Fe(OH)3
E I need help
D
25 The molar solubility of NH4Cl increases as pH _____.

A increases
B decreases
C is unaffected by changes in pH
D I need help

A
26 The molar solubility of Na2CO3 increases as pH _____.

A increases
B decreases
C is unaffected by changes in pH

D I need help

B
27 Which of the following factors affect solubility?

A pH
B Formation of Complex Ions
C Common-Ion Effect
D A, B, and C are correct
E I need help

D
Precipitation
 Solubility Rules
The solubility rules and the Ksp are useful in determining qualitatively
if a reaction would produce a precipitate.

A quantitative component is added to the above reactions and is

discussed in the coming slides.

In general:

Any salt made with a Group I metal is soluble.

All salts containing the nitrate ion are soluble.

All salts containing ammonium ion are soluble.

+ 2+ 2+
The majority of Ag , Pb , Hg cations are expected to be insoluble.
 Precipitation

In nature, metals are usually found as metal ores.

The metal contained in these ores are in the form of insoluble salts.

Making extraction even more difficult, the ores often contain several
metal salts.

Differences in the solubility of salts is used to selectively separate the

metal ions as precipitates of simple metal salts.
 Precipitation
+ 2+ 2+
Consider a test tube that contains Ag , Pb and Cu ions in
solution to be selectively separated from each other.

A suitable reagent can be add to the test tube that will form a
precipitate with one or more of the cations and leave the others in
solution.

The knowledge of the solubility rules or Ksp values for various metal
salts helps to accomplish this goal.
 Precipitation
+ 2+ 2+
Ag and Pb readily form insoluble salts and Cu does not form
insoluble salts as readily.
The Ksp value exists only if the salt is considered insoluble.

Salt Ksp Notice that CuCl2 is not to be found. This

Ag2S 6 x 10
-51 means CuCl2 is a soluble salt!
-28
PbS 3 x 10 + 2+
The Ag and Pb ions can be
-37
CuS 6 x 10 precipitated as chlorides as they have low
AgCl 1.8 x 10
-10 Ksp values indicating they are insoluble
-5
PbCl2 1.7 x 10
 Precipitation
- + 2+
Adding Cl should precipitate the Ag and Pb ions as the
2+
corresponding chlorides but not the Cu ions.
AgCl and PbCl2 can be removed from the test tube. Now, how can
we separate the AgCl and PbCl2 from the solid precipitate?

Salt Ksp Do you notice the significant difference

Ag2S 6 x 10
-51 between the Ksp values for Ag2S and
-28
PbS?
PbS 3 x 10 With more control on the concentrations
-37 2-
CuS 6 x 10 of S ions added, precipitation of one
-10 of the salts before the other can be
AgCl 1.8 x 10
accomplished.
-5
PbCl2 1.7 x 10
 Precipitation
So far the consideration was on dissolving the solids in solutions.
Consider the reverse process of formation of a solid or precipitation
from a solution.
When solutions are mixed, we can predict if a precipitation occurs or
not.
This can be explained with the help of an equation similar to Ksp.
This equation is known as the Ionic product, Q.
The ionic product Q (similar to reaction quotient) for solid CaF2 is
given:
2+ -
CaF2(s) Ca (aq) + 2 F (aq)
↔ 2+ - 2
Q = [Ca ]i [F ]i
It is the same as that of Ksp except that initial concentrations are
used instead of equilibrium concentrations for calculating Q.
 Precipitation
CaF2(s) ↔ Ca (aq) + 2 F (aq)
2+ -
2+ - 2
Q = [Ca ]i [F ]i
2+
When a solution containing Ca ions is mixed with another solution
-
containing F ions, the precipitate may or may not form.
The precipitation depends on the concentrations of these ions in the
solution.
Comparison of Q and Ksp values help to predict the precipitation.
If Q > Ksp, precipitation occurs to the point where the [ions] are
reduced to the point that they satisfy Ksp.
If Q < Ksp, no precipitation occrs.
 Precipitation
In order for a precipitate to form the equilibrium that exists between
the solution and the insoluble salt must reside on the left.

The Q value determines to which side the equilibrium will shift.

If Q = Ksp If Q > Ksp If Q < Ksp

A precipitate is
No precipitate is formed;
The solution is formed as the
there are so few cations
saturated without any number of cations
and anions that they all
undissolved solid. and anions exceeds
remain dissolved
the solubility

In a solution, when
Q = Ksp, the system is at equilibrium and the solution is saturated.
Q > Ksp, the salt will precipitate until Q = Ksp.
Q < Ksp, more solid can dissolve until Q = Ksp.
 Example 1: Precipitation
+ 2+
To a solution containing 0.100 M concentrations of Ag and Pb
ions, a 0.200 M K2S solution is slowly added.
a) What are the possible net ionic reactions in the solution?
b) Which solid will precipitate first out of the solution?
-51
Ksp of Ag2S = 6.0 x 10
-28
Ksp of PbS = 3.0 x 10
 Example 1: Precipitation
+ 2+
To a solution containing 0.100 M concentrations of Ag and Pb
ions, a 0.200 M K2S solution is slowly added.
a) What are the possible net ionic reactions in the solution?
-51
Ksp of Ag2S = 6.0 x 10
-28
Ksp of PbS = 3.0 x 10

2Ag (aq) + S (aq) ↔ Ag2S(s)

+ 2-
2+ 2-
Pb (aq) + S (aq) ↔ PbS(s)
 Example 1: Precipitation
+ 2+
To a solution containing 0.100 M concentrations of Ag and Pb
ions, a 0.200 M K2S solution is slowly added.
b) Which solid will precipitate first out of the solution?
-51
Ksp of Ag2S = 6.0 x 10
-28
Ksp of PbS = 3.0 x 10

Ag2S precipitation calculation:

+
Substitute [Ag ] in the Ksp expression.

-49
When the sulfide ion concentration is 6.0 x 10 M from the added K2S
solution, the silver sulfide will precipitate out.
 Example 1: Precipitation
+ 2+
To a solution containing 0.100 M concentrations of Ag and Pb
ions, a 0.200 M K2S solution is slowly added.
b) Which solid will precipitate first out of the solution?
-51
Ksp of Ag2S = 6.0 x 10
-28
Ksp of PbS = 3.0 x 10

PbS precipitation calculation:

2+
Substitute [Pb ] in the Ksp expression.

-27
When the sulfide ion concentration is 3.0 x 10 M from the added K2S
solution, the lead sulfide will precipitate out.
 Example 1: Precipitation
+ 2+
To a solution containing 0.100 M concentrations of Ag and Pb
ions, a 0.200 M K2S solution is slowly added.
b) Which solid will precipitate first out of the solution?
-51
Ksp of Ag2S = 6.0 x 10
-28
Ksp of PbS = 3.0 x 10

-49
The sulfide ion concentration needs to reach 6.0 x 10 M
before precipitating out as Ag2S and the sulfide ion
-27
concentration needs to reach 3.0 x 10 M before precipitating
out as PbS.
+
Since the sulfide ion concentration requirement is less for Ag
2+
than it is for Pb the silver sulfide will precipitate out first.
 Example 2: Precipitation
-5 -4
A solution contains 2.0 x 10 M barium ions and 1.8 x 10 M lead (II)
ions. If Na2CrO4 is added, which will precipitate first from solution?
-10
Ksp of BaCrO4 = 2.1 x 10
-13
Ksp of PbCrO4 = 2.8 x 10
 Example 2: Precipitation
-5 -4
A solution contains 2.0 x 10 M barium ions and 1.8 x 10 M lead (II)
ions. If Na2CrO4 is added, which will precipitate first from solution?
-10
Ksp of BaCrO4 = 2.1 x 10
-13
Ksp of PbCrO4 = 2.8 x 10

1. Determine which of the precipitation reaction(s) is(are) possible

and write the net ionic equation(s).
2+ 2+
Write equations for both Ba and Pb ions, to use them to calculate
which ion precipitates first:
Ba (aq) + CrO4 (aq) ↔ BaCrO4
2+ 2-

BaCrO4(s) ↔ Ba (aq) + CrO4 (aq)

2+ 2-

Pb (aq) + CrO4 (aq) ↔ PbCrO4

2+ 2-

PbCrO4(s) ↔Pb (aq) + CrO4 (aq)

2+ 2-
 Example 2: Precipitation
-5 -4
A solution contains 2.0 x 10 M barium ions and 1.8 x 10 M lead (II)
ions. If Na2CrO4 is added, which will precipitate first from solution?
-10
Ksp of BaCrO4 = 2.1 x 10 BaCrO4(s) ↔ Ba (aq) + CrO4
2+ 2-
-13
Ksp of PbCrO4 = 2.8 x 10 PbCrO (s) ↔Pb (aq) + CrO (aq)
2+ 2-
4 4

2. Write the Ksp expression for the selective precipitate based on the
Ksp values provided.
2+ 2- -10
Ksp =[Ba ][CrO4 ] = 2.1 x 10
2+ 2- -13
Ksp =[Pb ][CrO4 ] = 2.8 x 10
 Example 2: Precipitation
-5 -4
A solution contains 2.0 x 10 M barium ions and 1.8 x 10 M lead (II)
ions. If Na2CrO4 is added, which will precipitate first from solution?
-10
Ksp of BaCrO4 = 2.1 x 10 BaCrO4(s) ↔ Ba (aq) + CrO4 (aq)
2+ 2-
-13
Ksp of PbCrO4 = 2.8 x 10 PbCrO (s) ↔Pb (aq) + CrO (aq)
2+ 2-
4 4
2+
3. Calculate the cation, [Ba ],
concentration of the slightly
2-
soluble compound. 4. Calculate the anion, [CrO4 ],
concentration of the slightly
2+ -5
Given [Ba ] = 2.0 x 10 M soluble compound.
 Example 2: Precipitation
-5 -4
A solution contains 2.0 x 10 M barium ions and 1.8 x 10 M lead (II)
ions. If Na2CrO4 is added, which will precipitate first from solution?
-10
Ksp of BaCrO4 = 2.1 x 10 BaCrO4(s) ↔ Ba (aq) + CrO4 (aq)
2+ 2-
-13
Ksp of PbCrO4 = 2.8 x 10 PbCrO (s) ↔Pb (aq) + CrO (aq)
2+ 2-
4 4
2+
3. Calculate the cation, [Pb ],
concentration of the slightly
2-
soluble compound. 4. Calculate the anion, [CrO4 ],
concentration of the slightly
2+ -4
Given [Pb ] = 1.8 x 10 M soluble compound.
 Example 2: Precipitation
-5 -4
A solution contains 2.0 x 10 M barium ions and 1.8 x 10 M lead (II)
ions. If Na2CrO4 is added, which will precipitate first from solution?
-10
Ksp of BaCrO4 = 2.1 x 10 BaCrO4(s) ↔ Ba (aq) + CrO4 (aq)
2+ 2-
-13
Ksp of PbCrO4 = 2.8 x 10 PbCrO (s) ↔Pb (aq) + CrO (aq)
2+ 2-
4 4
5. Substitute the values into the reaction quotient (Q) expression.
This is the same expression as Ksp.

6. Compare Q to Ksp to determine whether a precipitate will form.

Steps 5 and 6 not used as Q is not calculated.

 Example 2: Precipitation
-5 -4
A solution contains 2.0 x 10 M barium ions and 1.8 x 10 M lead (II)
ions. If Na2CrO4 is added, which will precipitate first from solution?
-10
Ksp of BaCrO4 = 2.1 x 10 BaCrO4(s) ↔ Ba (aq) + CrO4 (aq)
2+ 2-
-13
Ksp of PbCrO4 = 2.8 x 10 PbCrO (s) ↔Pb (aq) + CrO (aq)
2+ 2-
4 4
7. The cation requiring the smaller amount of the anion indicates which
will precipitate first.

Compare the chromate ion concentration needed for each of the ions to
precipitate.
-8
The lead ion needs a smaller amount of the chromate ion [1.6 x 10 M]
-5
than the barium ion [1.05 x 10 M] to precipitate so PbCrO4 precipitates
first.
 Example 3: Precipitation
Will a precipitate form if 50.0 mL of 0.200 M barium chloride, BaCl2,
and 50.0 mL of 0.300 M sodium sulfate, Na2SO4 are mixed together ?
-10
Ksp of barium sulfate = 1.00 x 10
 Example 3: Precipitation
Will a precipitate form if 50.0 mL of 0.200 M barium chloride, BaCl2,
and 50.0 mL of 0.300 M sodium sulfate, Na2SO4 are mixed together ?
-10
Ksp of barium sulfate = 1.00 x 10
1. Determine which of the precipitation reaction(s) is(are) possible
and write the net ionic equation(s).

Ba (aq) + SO4 (aq) ↔ BaSO4

2+ 2-

BaSO4(s) ↔ Ba (aq) + SO4 (aq)

2+ 2-

2. Write the Ksp expression for the selective precipitate based on the
Ksp values provided.

-10
Given: Ksp of barium sulfate = 1.00 x 10
2+ 2-
Ksp = [Ba ][SO4 ]
 Example 3: Precipitation
Will a precipitate form if 50.0 mL of 0.200 M barium chloride, BaCl2,
and 50.0 mL of 0.300 M sodium sulfate, Na2SO4 are mixed together ?
-10
Ksp of barium sulfate = 1.00 x 10
BaSO4(s) ↔ Ba (aq) + SO4 (aq)
2+ 2-

2+
3. Calculate the cation, [Ba ], concentration of the slightly soluble
compound.
The total volume of the solution after mixing is 100 mL.
 Example 3: Precipitation
Will a precipitate form if 50.0 mL of 0.200 M barium chloride, BaCl2,
and 50.0 mL of 0.300 M sodium sulfate, Na2SO4 are mixed together ?
-10
Ksp of barium sulfate = 1.00 x 10
BaSO4(s) ↔ Ba (aq) + SO4 (aq)
2+ 2-

2-
4. Calculate the anion, [SO4 ], concentration of the slightly soluble
compound.
The total volume of the solution after mixing is 100 mL.
 Example 3: Precipitation
Will a precipitate form if 50.0 mL of 0.200 M barium chloride, BaCl2,
and 50.0 mL of 0.300 M sodium sulfate, Na2SO4 are mixed together ?
-10
Ksp of barium sulfate = 1.00 x 10
BaSO4(s) ↔ Ba (aq) + SO4 (aq)
2+ 2-

5. Substitute the values into the reaction quotient (Q) expression.

This is the same expression as Ksp, but instead of using equilibrium

concentrations, we are using the initial concentratiions to calculate Q.
 Example 3: Precipitation
Will a precipitate form if 50.0 mL of 0.200 M barium chloride, BaCl2,
and 50.0 mL of 0.300 M sodium sulfate, Na2SO4 are mixed together ?
-10
Ksp of barium sulfate = 1.00 x 10
BaSO4(s) ↔ Ba (aq) + SO4 (aq)
2+ 2-

6. Compare Q to Ksp to determine whether a precipitate will form.

-10;
Ksp = 1 x 10
Q= 0.015
Since Q > Ksp, there will be a precipitate formed when you mix equal
amounts of 0.20 M BaCl2, and 0.30 M Na2SO4.
28 What is the name of the solid precipitate that is formed
when a solution of sodium chloride is mixed with a
solution of silver nitrate?

A sodium silver

B sodium nitrate

C silver chloride

D Not enough information

C
E I need help
29 What is the name of the solid precipitate that is formed
when a solution of potassium carbonate is mixed with a
solution of calcium bromide?

A potassium bromide
B calcium carbonate
C potassium calcium
D not enough information
E I need help

B
↔
30 What is the name of the solid precipitate that is formed
when a solution of lead (IV) nitrate is mixed with a
solution of magnesium sulfate?

A PbSO4
B Pb(SO4)2
C Pb2SO4
D not enough information
E I need help
B

↔
 -4 + -3 2+
32 A solution contains 2.0 x 10 M Ag and 1.7 x 10 M Pb .
-
If NaCl is added. What concentration of Cl is needed to
-10
begin precipitation. AgCl (Ksp = 1.8 x 10 ) and PbCI2
-5
(Ksp = 1.7 x 10 )

-7
A 1.1 x 10 M
-2
B 8.5 x 10 M
-7
C 9.0 x 10 M
2
D 1.0 x 10 M C

E I need help
33 Will Co(OH)2 precipitate from solution if the pH of a 0.002
M solution of Co(NO3)2 is adjusted to 8.4? Ksp for Co(OH)2
-14
is 2.5 x 10 .

A Yes

B No
C I need help

B
↔
AP Style Problems
 AP Solubility Free Response 1
Silver chromate dissociates in water according to this equation:
+ 2- -12 o
Ag2CrO4(s) ↔ 2 Ag (aq) + CrO4 (aq) Ksp = 2.6 x 10 at 25 C
a) Write the equilibrium constant expression for the dissolving of
Ag2CrO4(s).
-1 +
b) Calculate the concentration, in mol L , of Ag (aq) in a saturated
o
solution of Ag2CrO4 at 25 C.
c) Calculate the maximum mass, in grams, of Ag2CrO4 that can
o
dissolve in 100. mL of water at 25 C.
d) A 0.100 mol sample of solid AgNO3 is added to a 1.00 L saturated
2-
solution of Ag2CrO4. Assuming no volume change, does [CrO4 ]
increase, decrease, or remain the same. Justify your answer.
 AP Solubility Free Response 1
Silver chromate dissociates in water according to this equation:
+ 2- -12 o
Ag2CrO4(s) ↔ 2 Ag (aq) + CrO4 (aq) Ksp = 2.6 x 10 at 25 C
a) Write the equilibrium constant expression for the dissolving of
Ag2CrO4(s).
+ 2 2-
Ksp = [Ag ] [CrO4 ]
-1 +
b) Calculate the concentration, in mol L , of Ag (aq) in a saturated
o
solution of Ag2CrO4 at 25 C.

+ 2-
Ag (aq) CrO4 (aq)
I 0 0
C +2x +x
E 2x x
 AP Solubility Free Response 1
Silver chromate dissociates in water according to this equation:
+ 2- -12 o
Ag2CrO4(s) ↔ 2 Ag (aq) + CrO4 (aq) Ksp = 2.6 x 10 at 25 C
c) Calculate the maximum mass, in grams, of Ag2CrO4 that can
o
dissolve in 100. mL of water at 25 C.
 AP Solubility Free Response 1
Silver chromate dissociates in water according to this equation:
+ 2- -12 o
Ag2CrO4(s) ↔ 2 Ag (aq) + CrO4 (aq) Ksp = 2.6 x 10 at 25 C
d) A 0.100 mol sample of solid AgNO3 is added to a 1.00 L saturated
2-
solution of Ag2CrO4. Assuming no volume change, does [CrO4 ]
increase, decrease, or remain the same. Justify your answer.

2- +
The [CrO4 ] will decrease. Adding [Ag ] will make Q > K.
To re-establish the equilibrium, the reaction goes from product
to reactant, decreasing Q.
 AP Solubility Free Response 2
o +
In a saturated solution of Ag3PO4 at 25 C, the concentration of Ag (aq) is
-5
5.3 x 10 M. The equilibrium constant expression for the dissolving of
+ 3 3-
Ag3PO4(s) in water is Ksp = [Ag ] [PO4 ].

a) Write the balanced equation for the dissolving of Ag3PO4 in water.

o
b) Calculate the value of Ksp for Ag3PO4 at 25 C.
c) A 1.00 L sample of saturated Ag3PO4 solution is allowed to evaporate
o +
at 25 C to a final volume of 500 mL. What is [Ag ] in the solution?Justify
your answer.
 AP Solubility Free Response 2
o +
In a saturated solution of Ag3PO4 at 25 C, the concentration of Ag (aq) is
-5
5.3 x 10 M. The equilibrium constant expression for the dissolving of
+ 3 3-
Ag3PO4(s) in water is Ksp = [Ag ] [PO4 ].

a) Write the balanced equation for the dissolving of Ag3PO4 in water.

+ 3-
Ag3PO4(s) ↔ 3 Ag (aq) + PO4
(aq)
o
b) Calculate the value of Ksp for Ag3PO4 at 25 C.
 AP Solubility Free Response 2
o +
In a saturated solution of Ag3PO4 at 25 C, the concentration of Ag (aq) is
-5
5.3 x 10 M. The equilibrium constant expression for the dissolving of
+ 3 3-
Ag3PO4(s) in water is Ksp = [Ag ] [PO4 ].

c) A 1.00 L sample of saturated Ag3PO4 solution is allowed to evaporate

o +
at 25 C to a final volume of 500 mL. What is [Ag ] in the solution?
Justify your answer.
+ -5
[Ag ] = 5.3 x 10 M
The [Ag+] in a saturated solution of Ag3PO4 is independent of the
volume of the solution.
 AP Solubility Free Response 3
Several reactions are carried out using AgBr, a cream-colored silver
−13
salt that has a solubility product constant, Ksp, of 5.0 x 10 .

a) Write the expression for the Ksp of AgBr.

+
b) Calculate the value of [Ag ] in 50.0 mL of a saturated solution of
AgBr.
c) A 50.0 mL sample of distilled water is added to the solution
described in part (b), which is in a beaker with some solid AgBr at the
bottom. The solution is stirred and equilibrium is reestablished. Some
+
solid AgBr remains in the beaker. Is the value of [Ag ] greater than,
less than, or equal to the value you calculated in part (b)? Justify your
answer.
d) Calculate the minimum volume of distilled water, in liters,
necessary to completely dissolve a 5.0 g sample of AgBr(s). The
-1
molar mass of AgBr is 188 g mol .
 AP Solubility Free Response 3
−4
e) A student mixes 10.0 mL of 1.5 x 10 M AgNO3 with 2.0 mL of 5.0
−4
x 10 M NaBr and stirs the resulting mixture. What will the student
observe? Justify your answer with calculations.
f) The color of another salt of silver, AgI(s), is yellow. A student adds a
solution of NaI to a test tube containing a small amount of solid,
cream-colored AgBr. After stirring the contents of the test tube, the
student observes that the solid in the test tube changes color from
cream to yellow.
i. Write the chemical equation for the reaction that occurred in the test
tube.
ii. Which salt has the greater value of Ksp: AgBr or AgI? Justify your
answer.
 AP Solubility Free Response 3
Several reactions are carried out using AgBr, a cream-colored silver
−13
salt that has a solubility product constant, Ksp of 5.0 x 10 .
a) Write the expression for the Ksp of AgBr.
+ -
Dissociation equation: AgBr(s) ↔ Ag (aq)+ Br (aq)
The solubility-product constant only takes into account the aqueous
−13 + -
ions, so Ksp = 5.0 x 10 = [Ag ][Br ]
 AP Solubility Free Response 3
Several reactions are carried out using AgBr, a cream-colored silver
−13
salt that has a solubility product constant, Ksp of 5.0 x 10 .
+
b) Calculate the value of [Ag ] in 50.0 mL of a saturated solution of
AgBr.

Since AgBr evenly dissociates into the two ions by a 1:1 ratio,
+ -
[Ag ] = [Br ].
 AP Solubility Free Response 3
Several reactions are carried out using AgBr, a cream-colored silver
−13
salt that has a solubility product constant, Ksp of 5.0 x 10 .
c) A 50.0 mL sample of distilled water is added to the solution
described in part (b), which is in a beaker with some solid AgBr at the
bottom. The solution is stirred and equilibrium is reestablished. Some
+
solid AgBr remains in the beaker. Is the value of [Ag ] greater than,
less than, or equal to the value you calculated in part (b)? Justify your
answer.
Since there is still solid at the bottom after adding the distilled
water, it is a saturated solution, both solutions are saturated.
+
Hence, the value of [Ag ] after addition of distilled water equals
-7
7.1 x 10 M (from part b). The concentration of ions in solution in
saturated equilibrium with a solid does not depend on the volume
of the solution, so the molar solubility is constant.
As long as the solution is saturated, evidenced by the solid
remaining, the ion concentration will be the same.
 AP Solubility Free Response 3
Several reactions are carried out using AgBr, a cream-colored silver
−13
salt that has a solubility product constant, Ksp of 5.0 x 10 .
d) Calculate the minimum volume of distilled water, in liters,
necessary to completely dissolve a 5.0 g sample of AgBr(s). The
-1
molar mass of AgBr is 188 g mol .
Since AgBr evenly dissociates into
the two ions by a 1:1 ratio,
+ -
[Ag ] must equal [Br ]
 AP Solubility Free Response 3
Several reactions are carried out using AgBr, a cream-colored silver
−13
salt that has a solubility product constant, Ksp of 5.0 x 10 .
−4
e) A student mixes 10.0 mL of 1.5 x 10 M AgNO3 with 2.0 mL
−4
of 5.0 x 10 M NaBr and stirs the resulting mixture. What will the
student observe? Justify your answer with calculations.
 AP Solubility Free Response 3
Several reactions are carried out using AgBr, a cream-colored silver
−13
salt that has a solubility product constant, Ksp of 5.0 x 10 .
−4
e) A student mixes 10.0 mL of 1.5 x 10 M AgNO3 with 2.0 mL
−4
of 5.0 x 10 M NaBr and stirs the resulting mixture. What will the
student observe? Justify your answer with calculations.

−13
Ksp is 5.0 x 10 . Since Q > Ksp, precipitation will occur, and AgBr
will precipitate as a cream colored solid.
 AP Solubility Free Response 3
Several reactions are carried out using AgBr, a cream-colored silver
−13
salt that has a solubility product constant, Ksp of 5.0 x 10 .
f) The color of another salt of silver, AgI(s), is yellow. A student adds
a solution of NaI to a test tube containing a small amount of solid,
cream-colored AgBr. After stirring the contents of the test tube, the
student observes that the solid in the test tube changes color from
cream to yellow.
i. Write the chemical equation for the reaction that occurred in the test
tube.
ii. Which salt has the greater value of Ksp: AgBr or AgI? Justify your
answer.
 AP Solubility Free Response 3
Several reactions are carried out using AgBr, a cream-colored silver
−13
salt that has a solubility product constant, Ksp of 5.0 x 10 .
f) The color of another salt of silver, AgI(s), is yellow. A student adds
a solution of NaI to a test tube containing a small amount of solid,
cream-colored AgBr. After stirring the contents of the test tube, the
student observes that the solid in the test tube changes color from
cream to yellow.
i. Write the chemical equation for the reaction that occurred in the test
tube.

Equilibrium equation: AgBr(s)+ NaI(aq) ↔ AgI(s) + NaBr(aq)

+ - + -
Net Ionic Equation: AgBr(s) + Na +I ↔ AgI(s) + Na +Br
- -
AgBr(s) + I (aq) ↔ AgI(s) + Br (aq)
Solid yellow colored AgI is precipitated.
 AP Solubility Free Response 3
Several reactions are carried out using AgBr, a cream-colored silver
−13
salt that has a solubility product constant, Ksp of 5.0 x 10 .
f) The color of another salt of silver, AgI(s), is yellow. A student adds
a solution of NaI to a test tube containing a small amount of solid,
cream-colored AgBr. After stirring the contents of the test tube, the
student observes that the solid in the test tube changes color from
cream to yellow.
ii. Which salt has the greater value of Ksp: AgBr or AgI? Justify your
answer.

The Ksp of AgBr is greater than the Ksp of AgI. In the presence
- -
of Br and I ions, the less soluble AgI precipitated. AgBr has a
greater Ksp value as less AgBr precipitated and more
dissociated into ions.
Ksp is directly proportional to the amount of ions produced.
 AP Solubility Free Response 4
A student knows from their solubility rules that silver chloride should
have very limited solubility in water at 25°C. To test this, they plan to
add 10.000 g of AgCl to a beaker with 1.0 L of distilled water. Then
they plan to filter the mixture and collect the solid undissolved AgCl
and expect it to be only slightly less than the original mass amount.
They carried out the experiment and collected these data:
Mass of filter paper: 2.3411 g
Mass of filter paper and collected AgCl: 12.3385 g
a) What is the molar solubility of AgCl?
b) What is the Ksp of AgCl?
c) How would the calculated value of Ksp be different if the student
-
used tap water (contains Cl ions) instead of distilled water? Explain.
d) If PbCl2 was used instead of AgCl, what is the expected mass of
-5
the filter paper and collected PbCl2? Ksp of PbCl2 is 1.70 x 10 .
 AP Solubility Free Response 4
Mass of filter paper: 2.3411 g
Mass of filter paper and collected AgCl: 12.3385 g
a) What is the molar solubility of AgCl?

Calculate the grams of AgCl collected: (12.3385 - 2.3411) g = 9.9974 g

The insoluble AgCl (precipitate) is not dissolved within the water so it is
caught by the filter paper.
mass of dissolved AgCl equals
the original mass of AgCl minus
the mass of the precipitate: molar solubility
(10.000 - 9.9974) g = .0026 g
dissolved AgCl
Convert this value to moles of molar solubility
AgCl to calculate the molar
solubility: molar solubility
 AP Solubility Free Response 4
Mass of filter paper: 2.3411 g
Mass of filter paper and collected AgCl: 12.3385 g
b) What is the Ksp of AgCl?

+ -
The equilibrium equation for AgCl is: AgCl(s) ↔ Ag (aq)+ Cl (aq)
The solubility-product constant only takes into account the
+ -
aqueous ions, so Ksp = [Ag ][Cl ]
-5
In part (a), we calculated Molar Solubility of AgCl = 1.81 x 10 M
+ - + -
Since Ag :Cl is a one to one ratio, [Ag ] = [Cl ]
 AP Solubility Free Response 4
Mass of filter paper: 2.3411 g
Mass of filter paper and collected AgCl: 12.3385 g
c) How would the calculated value of Ksp be different if the student
-
used tap water (contains Cl ions) instead of distilled water? Explain.

Since tap water is ionized and contains common ions with AgCl,
the common ion effect lowers the molar solubility and lowers
+ -
the Ksp. AgCl(s) ↔ Ag (aq) + Cl (aq)
-
Increases in initial amounts of Cl in the beginning of the
experiment will cause the equilibrium to shift to the rectant
causing more solid to precipitate out. Less ions would be
present in the solution phase. Solubility decreases due to the
common ion.
 AP Solubility Free Response 4
Mass of filter paper: 2.3411 g
Mass of filter paper and collected AgCl: 12.3385 g
d) If PbCl2 was used instead of AgCl, what is the expected mass of the
-5
filter paper and collected PbCl2? Ksp of PbCl2 is 1.70 x 10 .
Calculate molar solubility from the given Ksp value.
+2 -
The dissociation equation for PbCl2 is: PbCl2 ↔ Pb + 2Cl

-2
Thus, 1.62 x 10 moles of PbCl2
will dissolve & dissociate.

dissolved mass =

precipitate mass =
mass of paper
and precipitate =
 AP Solubility Free Response 5
-5
The molar solubility of ZnCO3 in distilled water is 1.21 x 10 M.

a) What is the Ksp for ZnCO3?

b) What is the molar solubility of ZnCO3 in 0.1 M ZnCl2?
c) Explain the difference in molar solubilities between the two solutions.
d) If the following changes were made to a saturated solution of ZnCO3
in distilled water, explain what would happen to the:
2+
i) concentration of Zn ions if water was evaporated.
ii) Ksp if water was evaporated.
iii) mole quantity of dissolved ions if additional distilled water was added.
iv) molar solubility of ZnCO3 if an aqueous solution of MnCl2 was added.
-11
The Ksp of MnCO3 is 2.24 x 10 .
 AP Solubility Free Response 5
-5
The molar solubility of ZnCO3 in distilled water is 1.21 x 10 M.
a) What is the Ksp for ZnCO3?

2+ 2-
Dissociation Equation: ZnCO3 (s) ↔ Zn (aq) + CO3 (aq)
2+ 2-
Ksp = [Zn ][CO3 ] since this is a 1:1 ratio of the ions.
 AP Solubility Free Response 5
-5
The molar solubility of ZnCO3 in distilled water is 1.21 x 10 M.
b) What is the molar solubility of ZnCO3 in 0.1 M ZnCl2?

2+
It is acceptable to use 0.1 M for the [Zn ] because it is so much
2+
larger than the Ksp that little Zn would be contributed from the
ZnCO3.

-9
Molar solubility of ZnCO3 = 1.46 x 10 M
 AP Solubility Free Response 5
-5
The molar solubility of ZnCO3 in distilled water is 1.21 x 10 M.
c) Explain the difference in molar solubilities between the two solutions.

The molar solubility of ZnCO3 in distilled water is greater than that in

ZnCl2.
2+
Since Zn acts as a common ion in the 0.1 M ZnCl2 solution, the
equilibrium is shifted reactant resulting in fewer dissociated ions
which contribute to the molar solubility.
 AP Solubility Free Response 5
-5
The molar solubility of ZnCO3 in distilled water is 1.21 x 10 M.
d) If the following changes were made to a saturated solution of ZnCO3
in distilled water, explain what would happen to the:
2+
i) concentration of Zn ions if water was evaporated.
2+
Nothing would happen to the concentration of Zn ions; the equilibrium
would simply shift left to dissipate the higher concentration created by
the evaporation of water. Since the solution remains saturated, the ratio
2+
of Zn ions and water left over is still constant (same concentration).
 AP Solubility Free Response 5
-5
The molar solubility of ZnCO3 in distilled water is 1.21 x 10 M.
d) If the following changes were made to a saturated solution of ZnCO3
in distilled water, explain what would happen to the:

ii) Ksp if water was evaporated.

Nothing would happen to the Ksp. The reaction will shift to a new
equilibrium position but the Ksp would be unaltered since the ion ratio
remains the same in the still saturated solution. Ksp will only be altered by
temperature change.
 AP Solubility Free Response 5
-5
The molar solubility of ZnCO3 in distilled water is 1.21 x 10 M.
d) If the following changes were made to a saturated solution of ZnCO3
in distilled water, explain what would happen to the:

iii) mole quantity of dissolved ions if additional distilled water was added.

The mole quantity of dissolved ions increases. The absolute number

of dissociated ions increases since added distilled water allows more
ZnCO3 to dissolve.
 AP Solubility Free Response 5
-5
The molar solubility of ZnCO3 in distilled water is 1.21 x 10 M.
d) If the following changes were made to a saturated solution of ZnCO3
in distilled water, explain what would happen to the:

iv) molar solubility of ZnCO3 if an aqueous solution of MnCl2 was added.

-11
The Ksp of MnCO3 is 2.24 x 10 .

The molar solubility of ZnCO3 increases since MnCO3 has a lower

2+
Ksp. The Mn ions will preferentially precipitate with the carbonate
ions, shifting the equilibrium to the right. ZnCO3 would have to
produce more ions to compensate the MnCO3 ions.
 AP Solubility Free Response 6
A student mixes 120.0 uL of 0.0020 M Ca(NO3)2 with 80.0 uL of 0.0040 M
NaF expecting to form a precipitate.

a. Write the proper net-ionic reaction for the expected reaction.

b. Predict whether the student should expect to form a precipitate or not.
-11
Justify this with a calculation. Ksp for CaF2(s) = 3.45 x 10 .
c. Agree or disagree with the following statements and justify your
answer:
i. Evaporating water from the mixture makes the precipitate more
likely to form.
ii. The ions remaining in solution in order of increasing concentration are
2+ - + -
Ca < F < Na < NO3 .
-9
d. Given that the Ksp for MgF2 is 3.50 x 10 , what is the Ksp for this
reaction?
2+ 2+
Mg (aq) + CaF2 (s) Ca (aq) + MgF2 (s)
 AP Solubility Free Response 6
A student mixes 120.0 uL of 0.0020 M Ca(NO3)2 with 80.0 uL of 0.0040 M
NaF expecting to form a precipitate.
a. Write the proper net-ionic reaction for the expected reaction.
2+ - - -
The ions present in solution are Ca , NO3 , Na and F . If this reaction
were to occur as a double displacement reaction, we would get both
NaNO3 and CaF2 as products.

Ca(NO3)2(aq) + 2 NaF(aq) 2 NaNO3(?) + CaF2(?)

+
Nitrate and Na compounds are soluble, so NaNO3 is soluble. Therefore,
the solid precipitate is the CaF2 compound.
Ca(NO3)2(aq) + 2 NaF(aq) 2 NaNO3(aq) + CaF2(s)
Then, write the net ionic equation as the formation of the solid (CaF2)
from its ions.
2+ -
Ca (aq) + 2 F (aq) CaF2(s)
 AP Solubility Free Response 6
A student mixes 120.0 uL of 0.0020 M Ca(NO3)2 with 80.0 uL of 0.0040 M
NaF expecting to form a precipitate.
b. Predict whether the student should expect to form a precipitate or not.
-11
Justify this with a calculation. Ksp for CaF2(s) = 3.45 x 10 .

Compare Q (initial reaction concentrations present) to Ksp to determine

whether or not a precipitate will form.
2+ -
To calculate initial concentrations, find moles of each Ca and F ion and
then find the concentrations in the combined solution.
 AP Solubility Free Response 6
A student mixes 120.0 uL of 0.0020 M Ca(NO3)2 with 80.0 uL of 0.0040 M
NaF expecting to form a precipitate.
b. Predict whether the student should expect to form a precipitate or not.
-11
Justify this with a calculation. Ksp for CaF2(s) = 3.45 x 10 .
2+ -
To calculate initial concentrations, find moles of each Ca and F and then
find the concentrations in the combined solution.
 AP Solubility Free Response 6
A student mixes 120.0 uL of 0.0020 M Ca(NO3)2 with 80.0 uL of 0.0040 M
NaF expecting to form a precipitate.
b. Predict whether the student should expect to form a precipitate or not.
-11
Justify this with a calculation. Ksp for CaF2(s) = 3.45 x 10 .
Compare Q (initial reaction concentrations present) to Ksp to determine
whether or not a precipitate will form.
2+ -
CaF2(s) Ca (aq) + 2 F (aq) (direction of Ksp reaction)
2+ - 2
Q for CaF2 = [Ca ] [F ]
-3 -3 2
Q =(1.2 x 10 )(1.6 x 10 )
-9 -11
Q = 3.0 x 10 Ksp = 3.45 x 10
Since Q > Ksp, the reaction will shift to the left (reverse of dissolving), so a
precipitate will form.
 AP Solubility Free Response 6
A student mixes 120.0 uL of 0.0020 M Ca(NO3)2 with 80.0 uL of 0.0040
M NaF expecting to form a precipitate.
c. Agree or disagree with the following statements and justify your
answer:
i. Evaporating water from the mixture makes the precipitate more
likely to form.
Evaporating water from the mixture
makes the precipitate more likely to
form by reducing the volume of the
mixture.

As shown by the red arrows in the

calculations, decreasing the volume
2+
of the mixture increases [Ca ] and
-
[F ], resulting in an increased Q. As
Q increases, the reaction becomes
more likely to form a precipitate.
 AP Solubility Free Response 6
A student mixes 120.0 uL of 0.0020 M Ca(NO3)2 with 80.0 uL of 0.0040 M
NaF expecting to form a precipitate.
c. Agree or disagree with the following statements and justify your
answer:
ii. The ions remaining in solution in order of increasing concentration are
2+ - + -
Ca < F < Na < NO3 .
- +
It is true that [NO3 ] > [Na ] because as verified by the below
calculations for these ions in the solution:
-3 - -6 -7 -
(4.0 x 10 M NO3 )(120.0 x 10 L) = 4.8 x 10 mol NO3
-7 - -3 -
(2.4 x 10 mol NO3 )/(200 uL) = 2.4 x 10 M NO3
-3 + -6 -7 +
(4.0 x 10 M Na )(80.0 x 10 L) = 3.2 x 10 mol Na
-7 + -3 +
(3.2 x 10 mol Na )/(200 uL) = 1.6 x 10 M Na
 AP Solubility Free Response 6
A student mixes 120.0 uL of 0.0020 M Ca(NO3)2 with 80.0 uL of 0.0040 M
NaF expecting to form a precipitate.
c. Agree or disagree with the following statements and justify your
answer:
ii. The ions remaining in solution in order of increasing concentration are
2+ - + -
Ca < F < Na < NO3 .
- 2+
As calculated in step (b), there are more ions of F than Ca
-
present in the solution. But, since 2 moles of F are required
2+ -
react with every 1 mole of Ca , F is the limiting reactant, so
there will be a smaller concentration at equilibrium.
- 2+
Therefore, the order given is incorrect. [F ] < [Ca ]
 AP Solubility Free Response 6
A student mixes 120.0 uL of 0.0020 M Ca(NO3)2 with 80.0 uL of 0.0040
M NaF expecting to form a precipitate.
-9
d. Given that the Ksp for MgF2 is 3.50 x 10 , what is the Ksp for this
reaction? 2+ 2+
Mg (aq) + CaF2 (s) Ca (aq) + MgF2 (s)
Write the two net ionic equations that sum to the above reaction.
2+ -
(1) CaF2(s) Ca (aq) + 2 F (aq) Ksp
2+ -
(2) Mg (aq) + 2 F (aq) MgF2(s) 1/Ksp

When two equations are added,

the equilibrium constants are
multiplied. Since the MgF2
reaction occurs in the opposite
direction, the inverse of its Ksp is
used.
 AP Solubility Free Response 7
A student mixes 4.5 mL of 0.0020 M NaOH with 4.5 mL of 0.0010 M
Cd(NO3)2 expecting to form a precipitate:
a. Write the proper net-ionic reaction for the expected reaction.
b. Predict whether a precipitate will form. Justify this with a
-15
calculation. Ksp for Cd(OH)2(s) = 5.3 x 10 .
c. Agree or disagree with the following statements and justify your
answer:
i. Increasing the volume of the solutions added will make the
precipitate more likely to form.
ii. Increasing the concentration of the solutions added will make the
precipitate more likely to form.
iii. Draw a picture representing the relative amounts of ions left in
solution after the solutions have been mixed.
-8
d. Given that the Ksp for CdC2O4 is 1.4 x 10 , what is the K for the
reaction below:
2- -
Cd(OH)2(s) + C2O4 (aq) 2 OH (aq) + CdC2O4(s)
 AP Solubility Free Response 7
A student mixes 4.5 mL of 0.0020 M NaOH with 4.5 mL of 0.0010 M
Cd(NO3)2 expecting to form a precipitate:
a. Write the proper net-ionic reaction for the expected reaction.

If the reaction occurs as a double displacement reaction, the products

are NaNO3 and Cd(OH)2. NaNO3 is soluble so it will not form a
precipitate. Therefore the expected precipitate is Cd(OH)2.

2+ -
Cd(OH)2(s) Cd (aq) + 2 OH (aq)
 AP Solubility Free Response 7
A student mixes 4.5 mL of 0.0020 M NaOH with 4.5 mL of 0.0010 M
Cd(NO3)2 expecting to form a precipitate:
b. Predict whether a precipitate will form. Justify this with a
-15
calculation. Ksp for Cd(OH)2(s) = 5.3 x 10 .

Compare Q (initial reaction concentrations present) to Ksp to determine

whether or not a precipitate will form.
2+ -
To calculate initial concentrations, find moles of each Cd and OH ion
and then find the concentrations in the combined solution.
 AP Solubility Free Response 7
A student mixes 4.5 mL of 0.0020 M NaOH with 4.5 mL of 0.0010 M
Cd(NO3)2 expecting to form a precipitate:
b. Predict whether a precipitate will form. Justify this with a
-15
calculation. Ksp for Cd(OH)2(s) = 5.3 x 10 .
2+ -
To calculate initial concentrations, find moles of each Cd and OH ion
and then find the concentrations in the combined solution.
 AP Solubility Free Response 7
A student mixes 4.5 mL of 0.0020 M NaOH with 4.5 mL of 0.0010 M
Cd(NO3)2 expecting to form a precipitate:
b. Predict whether a precipitate will form. Justify this with a
-15
calculation. Ksp for Cd(OH)2(s) = 5.3 x 10 .

Compare Q (initial reaction concentrations present) to Ksp to determine

whether or not a precipitate will form.
2+ -
Cd (aq) + 2 OH (aq) Cd(OH)2(s)
2+ - 2
Q for Cd(OH)2 = [Cd ] [OH ]
-4 -3 2
Q =(5.0 x 10 )(1.0 x 10 )
-10 -15
Q = 5.0 x 10 Ksp = 5.3 x 10 Q > Ksp
Since Q > Ksp, the reaction will occur in the direction that forms a
precipitate.
 AP Solubility Free Response 7
A student mixes 4.5 mL of 0.0020 M NaOH with 4.5 mL of 0.0010 M
Cd(NO3)2 expecting to form a precipitate:
c. Agree or disagree with the following statements and justify your
answer:
i. Increasing the volume of the solutions added will make the
precipitate more likely to form.

Increasing the volume of solutions added will not make precipitate

more likely to form. The concentrations will not change, which is what
the Q and Ksp values are dependent on.

ii. Increasing the concentration of the solutions added will make the
precipitate more likely to form.

Increasing the concentration of solutions will increase the Q value,

making the reaction more favorable in the direction of forming more
precipitate
 AP Solubility Free Response 7
A student mixes 4.5 mL of 0.0020 M NaOH with 4.5 mL of 0.0010 M
Cd(NO3)2 expecting to form a precipitate:
c. Agree or disagree with the following statements and justify your
answer:
iii. Draw a picture representing the relative amounts of ions left in
solution after the solutions have been mixed.
+
Using the initial amounts, determine the number of moles of Na and
-
NO3 present, as they do not form products after they dissociate. The
calculations show that the number of moles is the same for each ion.

O -
Na+
O N
O

Based on stoichiometry and the number of O -

ions in solution (both in a 1:2 ratio), there are N
2+ - O
no Cd or OH ions present as they are used O Na+

in forming the precipitate.

 AP Solubility Free Response 7
A student mixes 4.5 mL of 0.0020 M NaOH with 4.5 mL of 0.0010 M
Cd(NO3)2 expecting to form a precipitate:
-8
d. Given that the Ksp for CdC2O4 is 1.4 x 10 , what is the K for the
-15
reaction below. Ksp for Cd(OH)2(s) = 5.3 x 10 .
2- -
Cd(OH)2(s) + C2O4 (aq) 2 OH (aq) + CdC2O4(s)
Write the net ionic equations:
- 2+
Cd(OH)2(s) 2 OH (aq) + Cd (aq)
2+ 2-
Cd (aq) + C2O4 (aq) CdC2O4(s)
Multiply the Ksp values for
CdC2O4 and Cd(OH)2. Since
the Ksp expression is written in
the direction of the solid
dissociating, the Ksp value for
CdC2O4 is inverted because the
reaction, as written, is occurring
in the opposite direction.
The Free Energy of Dissolution (ΔG°diss)

The free energy of dissolution, (ΔGdiss) is the thermodynamic

parameter that characterizes the spontaneity of a dissolution
process e.g. NaCl (s) → Na+ (aq) + Cl– (aq)
It is represented by the equation

ΔG°diss = ΔH°diss −TΔS°diss

ΔH°diss = the enthalpy change

ΔS°diss = the entropy change
T = temperature in Kelvin
If the value for ΔGdiss is negative then dissolution is
thermodynamically favourable If the value for ΔGdiss is positive
then dissolution is not thermodynamically favourable
The dissolution process is driven by Enthalpic contributions
Entropic contributions or both of these
How does a solid dissolve?
There are three parts to a solid dissolving

Step 1: ΔH1 and ΔS1

step-1

Breaking the solid

This step involves breaking the solid apart by overcoming

the electrostatic forces between the ions
This requires energy, which means that ΔH1 is an
endothermic process with a positive value
Since disorder is increasing, ΔS1 will also be a positive
value
Step 2: ΔH2 and ΔS2

Solvent preparing to dissolve the solid

This step involves the solvent being prepared to
dissolve the solid
To make room for the solvent, the water molecules
must move apart by overcoming the hydrogen bonds in
water
This requires energy, which means that ΔH2 is an
endothermic process with a positive value
Since disorder is increasing, ΔS2 will be a positive
value
Step 3: ΔH3 and ΔS3

Formation of ion-dipole forces between the ions and water molecules

The final step involves the formation of ion-dipole interactions
between the water molecules and the ion
O atoms form a ion-dipole interaction with positive ions
H atoms form a ion-dipole interaction with negative ions
Since bonds are formed, ΔH3 is an exothermic process with a
negative value In this step, the entropy change will actually be
negative This is because of the attraction between the water
molecules and ions So there is decreased freedom of movement and
therefore number of microstates that can be formed
Enthalpy Change ΔH°diss
The enthalpy change during dissolution accounts for the heat
absorbed or released in the process
If heat is absorbed, the dissolution is endothermic (ΔHdiss > 0)
If heat is released, the dissolution is exothermic (ΔHdiss < 0)
Entropy Change, ΔS°diss
Entropy represents the degree of disorder in a system. An
increase in entropy (ΔSdiss > 0) signifies a more disordered state
This fits in well with dissolution as the state change is from (s) to
(aq) which represents an increase in disorder
NaCl (s) → Na+ (aq) + Cl– (aq)
Temperature
While a process might be not thermodynamically favourable at low
temperatures, an increase in temperature can make it
thermodynamically favourable