CHEM 113 Solubility

CHEM 113
Solubility
Copyright © Cengage Learning. All rights reserved. 17 | 1

Solubility
The maximum quantity of the substance,
expressed in grams, that will dissolve in a
certain solvent at a specific temperature.
S-C-9-1_Solubility Presentation
Solute + Solvent = Solution
• Solution – a homogeneous mixture of two or
more substances of ions or molecules
• Solute – the part of a solution that is being
dissolved (usually the lesser amount)
• Solvent – the part of a solution that dissolves
the solute (usually the greater amount)
Salt
Water Salt
(Solution) (Solute)
Water
(Solvent)
Types of Solutions
• Saturated – a solution that contains the maximum
quantity of solute that dissolves at that temperature.
• Unsaturated – a solution that contains less than the
maximum amount of solute that can dissolve at a
particular temperature.
• Supersaturated – a solution that contains more
solute than a saturated solution.
– Supersaturated solutions can be attained by heating the
solution up to dissolve more solute at that higher
temperature and then letting the solution cool.
– Once cooled, agitation causes crystals to precipitate
(separate from solution) out of the super saturated
solution.
UNSATURATED
SUPERSATURATED
SOLUTION
SOLUTION
more solute can becomes unstable, crystals
dissolve SATURATED form
SOLUTION
no more solute can
dissolve at given
temperature
increasing concentration
Solubility and Temperature
Increasing the temperature of a solvent speeds up the

particle movement. This causes more solvent
particles to bump into the solute, resulting in solute
particles breaking loose and dissolving faster.
Solubility Curve
A graph of the solubility of a compound (grams/100

grams water on the Y-axis) at various temperatures
(Celsius on X- axis). Each compound has a different
curve.
Solubility vs. Temperature for Solids and gases
Solubility Curve 140
KI
Graph 130
120
*Solubility is
Solubility (grams of solute/100 g H2O)

110 NaNO3 gases
dependent 100
solids
on temperature 90
KNO3
80
HCl NH4Cl
What trends do you 70
60 NH3
see on the graph? 50
KCl
40
How is the solubility 30

NaCl KClO3
20
of gases and solids 10
different? SO2
0 10 20 30 40 50 60 70 80 90 100
Temperature °C
Solubility vs. Temperature for Solids
140
KI
130
If you stir faster, 120
Solubility (grams of solute/100 g H2O)

NaNO3
will that make 110 gases
solids
you dissolve 100
90
KNO3
more? 80
HCl NH4Cl
70
No, it allows you to dissolve 60 NH3 KCl

substances faster but not 50
more. Increasing the 40
temperature does 30
NaCl KClO3
allow you to dissolve more. 20
10
SO2
0 10 20 30 40 50 60 70 80 90 100
Temperature
Solubility vs. Temperature
Saturated!
• What term describes
39g NaCl at 70C?
Unsaturated
• What about 30g at
the same
temperature?
Supersaturated
• What about 45g at
the same
temperature?
Solids dissolved in liquid Gases dissolved in liquids
Sol.
Sol.
To
To
As To solubility As To solubility
Solids are more soluble at...higher temperatures.
Gases are more soluble at...lower temperatures &

higher pressures.
Solutions con
2. Pressure
For solid solutes: as pressure increases,
solubility remains the same.
For gas solutes: as pressure increases,
solubility increases
3. Nature of Solute/Solvent
“Like dissolves in like.”
Solute/Solvents cont.
Solubility Summary
Solute Type Nonpolar Polar Solvent
solvent
Nonpolar (Fat Soluble (soap) Insoluble
Grease) (water)
Polar Insoluble Soluble (water)
Ionic (salt) insoluble Soluble (water)
High solubility-soluble Low solubility-insoluble

Solubility Rules
• Not all ionic compounds are water soluble
• There are some general rules for compounds
that are water soluble:
– Group 1 ionic compounds and ammonium
(NH4+) are always water soluble
– Group 17 ionic compounds are water
soluble except when paired with Ag, Pb,
and Hg ions
General Rules for the Solubility of Ionic Compounds
•A compound is soluble if it contains one of the following cations:
-Group 1A cations: Li+, Na+, K+, Rb+, Cs+
-Ammonium, NH4+
•A compound is soluble if it contains one of the following
anions:
-Halide: Cl-, Br-, I-, except for salts with Ag+, Hg22+, Pb+2
-Nitrate, NO3-
-Acetate, CH3CO2-
-Sulfate, SO42-, except for salts with Ba+2, Hg22+, Pb+2
Examples
• AgNO3 = water soluble

• AgCl = insoluble
• Na2S = soluble
• NaCl = soluble
• CaCO3 = insoluble
• AlPO4 = insoluble
Do Now: label as soluble and insoluble
1. CH4 - Insoluble
2. AgCl - Insoluble
- soluble
3. C12H22O11
- soluble
4. NaNO3
- soluble
5. KOH
Precipitation reactions
• Recall that double-replacement reactions have

the general formula:
AB(aq) + CD(aq) AD(aq) +CB(s)
A precipitation reaction will take place if one or
both of the products is listed as an insoluble
solid.
2KI(aq) + Pb(NO3)2(aq) -> 2KNO3(aq) + PbI(s)
• KI = soluble
• Pb(NO3)2 = soluble
• 2KNO3(aq) = soluble
• PbI(s) = insoluble solid
• In a precipitation reaction, two clear aqueous
solutions are combined to form a cloudy, solid
precipitate that can be collected by filtration.
Solubility Equilibria
• Because ionic compounds are strong electrolytes,
they dissociate completely to the extent that they
dissolve.
• When an equilibrium equation is written, the solid
is the reactant and the ions in solution are the
products.
• The equilibrium constant expression is called the
solubility-product constant. It is represented as
Ksp.
When an ionic compound is insoluble or slightly
soluble, an equilibrium is established:
MX(s) M+(aq) + X−(aq)
The equilibrium constant for this type of reaction is

called the solubility−product constant, Ksp.
For the above reaction,

Ksp = [M+][X−]

Solubility Product
 For example:
BaSO4(s) ⇌ Ba2+(aq) + SO42–(aq)
 The equilibrium constant expression is
Ksp = [Ba2+][SO42]
 Another example:
Ba3(PO4)2(s) ⇌ 3 Ba2+(aq) + 2 PO43–(aq)
 The equilibrium constant expression is
Ksp = [Ba2+]3[PO43]2
Solubility Equilibria
• Solubility product (Ksp) – equilibrium constant; has

only one value for a given solid at a given
temperature.
• Solubility – an equilibrium position.
Bi2S3(s) 2Bi3+(aq) + 3S2–(aq)

2 2 3
K sp = Bi  S 
3+
Copyright © Cengage Learning. All rights reserved 22

Solubility vs. Solubility Product
• Ksp is not the same as solubility.
• Solubility is the quantity of a substance that dissolves
to form a saturated solution (reach equilibrium)
• Common units for solubility:
 Grams per liter (g/L)
 Moles per liter (mol/L)
?
Write the solubility−product expression for
the following salts:
a. Hg2Cl2
b. HgCl2

a. Hg2Cl2
Hg2Cl2(s) 2Hg+(aq) + 2Cl−(aq)
Ksp = [Hg+]2[Cl−]2
b. HgCl2
HgCl2(s) Hg2+(aq) + 2Cl−(aq)
Ksp = [Hg2+][Cl−]2

?
Exactly 0.133 mg of AgBr will dissolve in
1.00 L of water. What is the value of Ksp for
AgBr?
Solubility equilibrium:
AgBr(s) Ag+(aq) + Br−(aq)
Solubility−product constant expression:

Ksp = [Ag+][Br−]

The solubility is given as 0.133 mg/1.00 L, but Ksp uses
molarity:
0.133  103 g 1 mol 7
  7.083  10 M
1.00 L 187.77 g
AgBr(s)  Ag+(aq) + Br−(aq)
Initial 0 0
Change +x +x
Equilibrium x x

[Ag+] = [Cl−] = x = 7.083 × 10−7 M
Ksp = (7.083 × 10−7)2
Ksp = 5.02 × 10−13

An experimenter finds that the solubility of
? barium fluoride is 1.1 g in 1.00 L of water

at 25°C. What is the value of Ksp for
barium fluoride, BaF2, at this temperature?
BaF2(s) Ba2+(aq) + 2F−(aq)

Ksp = [Ba2+][F−]2

The solubility is given as 1.1 g/1.00 L, but Ksp uses
molarity:
1.1 g 1 mol
x   6.27  10 3 M
1.00 L 175.32 g
BaF2(s)  Ba2+(aq) + 2F−(aq)
Initial 0 0
Change +x +2x
Equilibrium x 2x
[Ba2+] = x = 6.27 × 10−3 M
[F−] = 2x = 2(6.27 × 10−3) = 1.25 × 10−2 M
Ksp = (6.27 × 10−3)(1.25 × 10−2)2
Ksp = 9.8 × 10−7

When Ksp is known, we can find the molar solubility.

Calomel, whose chemical name is
? mercury(II) chloride, HgCl2, was once used

in medicine (as a laxative and diuretic).
It has a Ksp equal to 1.3  1018.
What is the solubility of HgCl2 in grams
per liter? Mr (HgCl2) = 472.086 g/mol
HgCl2(s) Hg2+(aq) + 2Cl−(aq)

Ksp = [Hg2+][Cl−]2
HgCl2(s)  Hg2+(aq) + 2Cl−(aq)
Initial 0 0
Change +x +2x
Equilibrium x 2x
Ksp = x(2x)2
Ksp = x(4x2)
Ksp = 4x3
1.3 × 10−18 = 4x3
x3 = 3.25 × 10−19
x = 6.88 × 10−7 M
The molar solubility is 6.9 × 10−7 M, but we also need the
solubility in g/L:
6.88  10 -7 mol 472.086 g

  3.2  10  4 g/L
L 1 mol
 0.32 mg/L

Concept Check
Lead compounds have been used as paint pigments, but because the
lead(II) ion is toxic, the use of lead paints in homes is now prohibited.
Which of the following lead(II) compounds would yield the greatest
number of lead(II) ions when added to the same quantity of water
(assuming that some undissolved solid always remains): PbCrO4,
PbSO4, or PbS?
We can begin by identifying the value of Ksp for each compound:
Each salt produces two ions, so each has the same expression for
the solubility−product constant: Ksp= x2.
PbCrO4 1.8 × 10−14
PbSO4 1.7 × 10−8
PbS 2.5 × 10−27
The solubility will be largest for PbSO4.

Factors that affect solubility
• Temperature
– Solubility generally increases with temperature;
• Common ion effect
– Common ions reduce solubility
• Salt effect
– This slightly increases solubility
• pH of solution
– pH affects the solubility of ionic compounds in which
the anions are conjugate bases of weak acids;
• Formation of complex ion
– The formation of complex ion increases solubility
What effect does the presence of a common ion have on
solubility?
Given: MX(s) M+(aq) + X−(aq)
Qualitatively, we can use Le Châtelier’s principle to

predict that the reaction will shift in the reverse
direction when M+ or X− is added, reducing the
solubility.
In the next problem, we will explore this situation

quantitatively.

Common Ion Effect
• Consider the following solubility equilibrium:
• AgCl(s) ⇌ Ag+(aq) + Cl-(aq); Ksp = 1.6 x 10-10;
• The solubility of AgCl is 1.3 x 10-5 mol/L at 25oC.

• If NaCl is added, equilibrium shifts left due to
increase in [Cl-] and some AgCl will precipitate out.
• For example, if [Cl-] = 1.0 x 10-2 M,
• Solubility of AgCl = (1.6 x 10-10)/(1.0 x 10-2)
• = 1.6 x 10-8 mol/L
Effect of pH on Solubility
• Consider the following equilibrium:

Ag3PO4(s) ⇌ 3Ag+(aq) + PO43-(aq);
• If HNO3 is added, the following reaction occurs:

H3O+(aq) + PO43-(aq) ⇌ HPO42-(aq) + H2O
• This reaction reduces PO43- in solution, causing more
solid Ag3PO4 to dissolve.
• In general, the solubility of compounds such as
Ag3PO4, which anions are conjugate bases of weak
acids, increases as the pH is lowered by adding nitric
acid.
• Consider the following equilibrium:

Mg(OH)2(s) ⇌ Mg2+(aq) + 2 OH-(aq);
• Increasing the pH means increasing [OH-] and

equilibrium will shift to the left, causing some of
Mg(OH)2 to precipitate out.
• If the pH is lowered, [OH-] decreases and equilibrium
shifts to the right, causing solid Mg(OH)2 to dissolve.
• The solubility of compounds of the type M(OH)n
decreases as pH is increased, and increases as pH is
decreased.
What is the molar solubility of silver
? chloride in 1.0 L of solution that contains

2.0  102 mol of HCl?
First, we find that the Ksp for AgCl at 25°C is 1.8 ×

10−10.
Next, we construct the ICE chart with the initial [Cl−] =

0.020 M. We then solve for x, the molar solubility.

AgCl(s)  Ag+(aq) + Cl−(aq)
Initial 0 0.020
Change +x +x
Equilibrium x 0.020 + x
Ksp = [Ag+][Cl−]
1.8 × 10−10 = x(0.020 + x)
We make the following simplifying assumption: 0.020 +
x  0.020.
1.8 × 10−10 = 0.020x
The molar solubility is given by x:
x = 9.0 × 10−9 M
Let’s compare this result to the solubility of AgCl in water:

Ksp = x2
1.8 × 10−10 = x2
x = 1.3 × 10−5 M
The solubility was reduced by a factor of about 1400!

Solubility Exercise #1
Calculate the solubility of AgCl in water and in 1.0

M NH3 solution at 25oC. Ksp = 1.6 x10-10
• Solutions:
Solubility in water = (Ksp)
= (1.6 x 10-10) = 1.3 x 10-5 mol/L
• Solubility of AgCl in 1.0 NH3:

• AgCl(s) + 2NH3(aq) ⇌ Ag(NH3)2+(aq) + Cl-(aq)

• [Initial], M - 1.0 0.0 0.0
• [Change] - -2S +S +S
• [Equilm.] - (1 – 2S) S S


[Ag(NH 3 ) 2 ][Cl - ] S2
K net    2.7 x 10 -3
[ NH 3 ]2 (1 - 2 S ) 2
• Solubility of AgCl in 1.0 NH3 (continued):

S
 2.7 x 10 -3  0.052
(1 - 2 S )
• S = 0.052 – 0.104S;
• S = 0.052/1.104 = 0.047 mol/L
• AgCl is much more soluble in NH3 solution than in
water.
AgCl in water = 1.3 x 10-5 mol/L

We can use the reaction quotient, Q, to determine whether
precipitation will occur.

Predicting Formation of Precipitate
• Qsp = Ksp  saturated solution, but no precipitate

• Qsp > Ksp  saturated solution, with precipitate
• Qsp < Ksp  unsaturated solution,
• Qsp is ion product expressed in the same way as Ksp

for a particular system.
One form of kidney stones is calcium
? phosphate, Ca3(PO4)2, which has a

Ksp of 1.0  1026.
A sample of urine contains 1.0  103 M
Ca2+ and 1.0  108 M PO43 ion.
Calculate Qc and predict whether Ca3(PO4)2
will precipitate.

Ca3(PO4)2(s) 3Ca2+(aq) + 2PO43−(aq)
Ksp = [Ca2+]3 [PO43−]2
Ksp = 1.0 × 10−26
Qc = (1.0 × 10−3)3 (1.0 × 10−8)2
Qc = 1.0 × 10−25
Ksp < Qc
A precipitate will form.
When a problem gives the amounts and concentrations
of two samples that are then mixed, the first step in
solving the problem is to calculate the new initial
concentrations.

Exactly 0.400 L of 0.500 M Pb2+ and 1.60 L
? of 2.50  102 M Cl are mixed together to

form 2.00 L of solution.
Calculate Qc and predict whether PbCl2
will precipitate.
Ksp for PbCl2 is 1.6  105.

2 (0.500 M ) (0.400 L)
[Pb ]   0.100 M
(2.00 L)
 (2.50  10 -2
M) (1.60 L)
[Cl ]   0.0200 M
(2.00 L)
PbCl2(s) Pb2+(aq) + 2Cl−(aq)
Ksp = [Pb2+] [Cl−]2 = 1.6 × 10−5
Qc = (0.100)(0.0200)2 = 4.00 × 10−5
Ksp < Qc
A precipitate will form.
17 | 54
When a salt contains the conjugate base of a weak acid,
the pH will affect the solubility of the salt.

We will qualitatively explore the situation involving a
generic salt, MX, where X is the conjugate base of a
weak acid.
MX(s) M+(aq) + X−(aq)
As the acid concentration increases, X− reacts with the

H3O+, forming HX and reducing the X− concentration.
As a result, more MX dissolves, increasing the
solubility.

Consider the two slightly soluble salts
? barium fluoride and silver bromide. Which

of these would have its solubility more
affected by the addition of strong acid?
Would the solubility of that salt increase or
decrease?
HF is a weak acid, while HBr is a strong acid.

BaF2 is more soluble in an acidic solution.
AgBr is unaffected by an acidic solution.

Ksp for MgC2O4 is 8.5 × 10−5.
Ksp for CaC2O4 is 2.3 × 10−9.
MgC2O4 is more soluble.
If a dilute acidic solution is added, it will increase the

solubility of both salts. MgC2O4 is still more soluble.

Fractional Precipitation
• The method of precipitating some ions from a

solution while leaving others in solution is called
fractional precipitation.
– If a solution contains Cu+, Ag+, and Au+, each ion
can be precipitated as chlorides.
 
CuCl  Cu  Cl 
K sp  Cu Cl   1.9  10
  7
 
AgCl  Ag  Cl 
K sp   Ag Cl   1.8  10
  10
 
AuCl  Au  Cl 
K sp   Au Cl   2.0  10
  13
59
Example : If solid sodium chloride is slowly added to a

solution that is 0.010 M each in Cu+, Ag+, and Au+
ions, which compound precipitates first? Calculate
the concentration of Cl- required to initiate
precipitation of each of these metal chlorides.
60
• These three calculations give the [Cl-] required
to precipitate AuCl ([Cl-] >2.0 x 10-11 M), to
precipitate AgCl ([Cl-] >1.8 x 10-8 M), and to
precipitate CuCl ([Cl-] >1.9 x 10-5 M).
• It is also possible to calculate the amount of
Au+ precipitated before the Ag+ begins to
precipitate, as well as the amounts of Au+ and
Ag+ precipitated before the Cu+ begins to
precipitate.
61
Example : Calculate the percentage of Au+ ions that

precipitate before AgCl begins to precipitate.
– Use the [Cl-] from Example to determine the [Au +]
remaining in solution just before AgCl begins to precipitate.
62
It is possible to use these differences to separate
compounds.
This is common practice when the goal is to separate

sulfides from one another.
The qualitative analysis scheme for the separation of

metal ions uses sulfide solubility to separate Co2+, Fe2+,
Mn2+, Ni2+, and Zn2+ (Analytical Group III).

The combination of solubility and complex−ion
equilibria can be applied to separate metal ions.
Cations can be separated into groups according to

their precipitation properties.
In each major step, one group of cations

precipitates out. After separating the precipitate,
the remaining solution is treated with the next
reagent, precipitating the next group of cations.

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CHEM 113

Copyright © Cengage Learning. All rights reserved. 17 | 1

Increasing the temperature of a solvent speeds up the

A graph of the solubility of a compound (grams/100

Solubility (grams of solute/100 g H2O)

What trends do you 70

How is the solubility 30

If you stir faster, 120

Solubility (grams of solute/100 g H2O)

you dissolve 100

No, it allows you to dissolve 60 NH3 KCl

more. Increasing the 40

Solids are more soluble at...higher temperatures.

Gases are more soluble at...lower temperatures &

High solubility-soluble Low solubility-insoluble

•A compound is soluble if it contains one of the following cations:

-Group 1A cations: Li+, Na+, K+, Rb+, Cs+

• AgNO3 = water soluble

• Recall that double-replacement reactions have

MX(s) M+(aq) + X−(aq)

The equilibrium constant for this type of reaction is

For the above reaction,

Copyright © Cengage Learning. All rights reserved. 17 | 20

• Solubility product (Ksp) – equilibrium constant; has

Bi2S3(s) 2Bi3+(aq) + 3S2–(aq)

Copyright © Cengage Learning. All rights reserved 22

Copyright © Cengage Learning. All rights reserved. 17 | 24

Copyright © Cengage Learning. All rights reserved. 17 | 25

Solubility−product constant expression:

Copyright © Cengage Learning. All rights reserved. 17 | 26

AgBr(s)  Ag+(aq) + Br−(aq)

Copyright © Cengage Learning. All rights reserved. 17 | 27

Ksp = (7.083 × 10−7)2

Ksp = 5.02 × 10−13

Copyright © Cengage Learning. All rights reserved. 17 | 28

? barium fluoride is 1.1 g in 1.00 L of water

Solubility−product constant expression:

Copyright © Cengage Learning. All rights reserved. 17 | 29

BaF2(s)  Ba2+(aq) + 2F−(aq)

[F−] = 2x = 2(6.27 × 10−3) = 1.25 × 10−2 M

Ksp = (6.27 × 10−3)(1.25 × 10−2)2

Ksp = 9.8 × 10−7

Copyright © Cengage Learning. All rights reserved. 17 | 31

Copyright © Cengage Learning. All rights reserved. 17 | 32

? mercury(II) chloride, HgCl2, was once used

Solubility−product constant expression:

6.88  10 -7 mol 472.086 g

Copyright © Cengage Learning. All rights reserved. 17 | 35

The solubility will be largest for PbSO4.

Given: MX(s) M+(aq) + X−(aq)

Qualitatively, we can use Le Châtelier’s principle to

In the next problem, we will explore this situation

Copyright © Cengage Learning. All rights reserved. 17 | 38

• The solubility of AgCl is 1.3 x 10-5 mol/L at 25oC.

• Consider the following equilibrium:

• If HNO3 is added, the following reaction occurs:

• Consider the following equilibrium:

• Increasing the pH means increasing [OH-] and