SOLUBILITY

EQUILIBRIUM
GROUP 3 – CHEMISTRY LECTURE
TABLE OF CONTENT
• Solubility equilibrium
• Solubility product
• Molar solubility and solubility
• The common-ion effect and solubility
• ph and solubility
• Complex-ion equilibrium and solubility
• Application of Solubility product principle to
qualitative analysis
 SOLUBILITY EQUILIBRIA
Before going, Lets know the basics:
A precipitation reaction refers to the formation of an insoluble salt when two solutions
containing soluble salts are combined.

The insoluble salt that falls out of solution is known as the precipitate, hence the
reaction’s name.

Solubility: The amount of a substance that will dissolve in a given amount of solvent to
give a saturated solution under specified conditions. Solubility is the ability of a solute
to dissolve in a solvent to form a solution.

A solution is considered saturated when adding additional solute no longer increases

the concentration of the solution.

The solubility of a chosen solute can be based off of a Solubility Table.

 SOLUBILITY EQUILIBRIA
Before this, Lets know the basics:
SOLUBILITY TABLE

the solubility of a substance can vary from essentially zero (insoluble or sparingly soluble)
to infinity (miscible). The term “insoluble” is often applied to poorly soluble compounds.
 SOLUBILITY EQUILIBRIA
Solubility equilibria are
Water as Solvent
established when the dissolution
AgCl(s) and precipitation of a solute
Silver Chloride species occur at equal rates.
as Solute
AB ßà (A)a + (B)b
EXAMPLE:
→
AgCl(s) Precipitate AgCl(s) → Ag+(aq) + Cl–(aq)
 SOLUBILITY EQUILIBRIA
WHAT HAPPENS IN THE BEAKER
Solubility Product is the
DISSOLUTION REACTION
equilibrium constant representing the
AgCl(s) → Ag+(aq) + Cl–(aq) maximum amount of solid that can be
REVERSE of the DISSOLUTION REACTION dissolved in aqueous solution.
Ag+(aq) + Cl–(aq) → AgCl(s) The Solubility Product of This Solution is

EQUILIBRIUM is reached
Ksp = [Ag+][Cl–]
→
AgCl(s) → Ag+(aq) + Cl–(aq) High Ksp means High Solubility.
Low Ksp means Low Solubility
 SOLUBILITY PRODUCT
HOW TO CALCULATE: ION
CONCENTRATION > Ksp
We have a saturated solution of Milk of Magnesia which is
Mg(OH)2 The Magnesium ion concentration is 3.7x10-5

Mg(OH)2 (S) ßà Mg+2(aq) + 2OH-(aq)

Ksp = [Mg+2] [OH-]2
[3.7x10-5] [2(3.7x10-5)]2
[3.7x10-5] [7.4x10-5]2
= 2.0x10-13
 SOLUBILITY PRODUCT
HOW TO CALCULATE: Ksp > ION
CONCENTRATION

Pbl2 is placed in water. If it has a Ksp of 7.9 x 10-9, what will be the concentration
of each ion?
Pbl2 (S) ßà Pb+2(aq) + 2I- Ksp of 7.9 x 10-9 = (x)(2x)2 = 4x3
(aq) _
(𝟕.𝟗𝒙𝟏𝟎 𝟗 )
Ksp = [Pb+2] + [I-]2 𝒙= ∛ = 1.3x10-3
𝟒
Ksp of 7.9 x 10-9 The solubility of the solid is 1.3x10-3
Pbl2 Pb+2(aq) 2I-(aq) Ksp = [Pb+2] [I-]2
Initial 0 0 [1.3x10-3] [1.3x10-3]2
Change +x +2x [1.3x10-3] [2.6x10-3]
Equilibrium x 2x [Pb+2] = 1.3x10-3 [I-]2 = 2.6x10-3
 MOLAR SOLUBILITY
Molar solubility - is the solubility product, it is
the number of Mol of the solute that can be dissolve
per liter of solution, before it becomes saturated.

Ksp or solubility product constant, is the

equilibrium constant for a solid substance dissolving in
an aqueous solution. It represents the level at which a
solute dissolves in solution. The more soluble a
substance is, the higher the Ksp value it has.
 MOLAR SOLUBILITY
Procedure on how to find the Ksp using Molar
Solubility:

Ex 1) the molar solubility of Ca(OH)2 is 6.875 x 10^-3 Mol/L. Calculate

the Ksp of Ca(OH)2.

First we need to do is express Ca(OH)2 into a chemical equilibrium

Ca(OH)2 (s) ⇌ Ca+2(aq) + 2OH– (aq)

Ca(OH)2 is 6.875x10-3 Mol/L – this is the concentration of
Ca(OH)2 that is dissolve in this solution
 MOLAR SOLUBILITY
Procedure on how to find the Ksp using Molar
Solubility:
The second step is to look at their Coefficient, the product Ca+2 and
OH-(Always pay attention to it). Multiply it with the given Molar
Solubility, individually.
Ca+2 = 6.875 x 10-3 = 6.875 x 10-3 M
OH- = 6.875 x 10-3 = 0.01375 M
Also in order to get the Molar concentration of OH- we can also use
Stoichiometry.
__2 Mol OH-_
6.875 x 10^-3 Mol Ca(OH)2 × =
1Mol Ca(OH)2
These are the Molar concentration of the Ca+2 and OH-
 MOLAR SOLUBILITY
Procedure on how to find the Ksp using Molar
Solubility:
Afterwards, we will express it in Ksp formula. By multiplying the value
of each product base on their coefficient. And then multiply both the
value of the product after.

Ksp = (Ca+2) × (OH-)²

Ksp = (6.875 x 10^-3) x (0.01375)²
Ksp = (6.875 x 10^-3) x (0.0275)
Ksp = 1.3x10-6 is the value of Ca(OH)2 solubility
product constant
 MOLAR SOLUBILITY
Finding Ksp with the given Molar solubility of
a product instead of the reactant.
Ex 2) the solubility of Ba+2 is 2.667 x 10-8 mol/L in a saturated
solution of Ba3(PO4)2. Calculate the Ksp of Ba3(PO4)2.

The first thing we do is express it into a chemical equilibrium

Ba3(PO4)2 (s) ⇌ 3Ba+2(aq) + 2PO4-3 (aq)
There's no need to find the Molar Solubility of Ba3(PO4)2 which is the
reactant, because we are already given a clue to solve for Ksp without
it. All we need to do is find the value of its fellow product the PO4-3
 MOLAR SOLUBILITY
Finding Ksp with the given Molar solubility of
a product instead of the reactant.
We will use Stoichiometry to find PO4-3.
2Mol PO4-3
2.667x10-8 Mol Ba+2 × = 1.778 x 10-8 M
3Mol Ba+2
Ba+2 = 2.667x10-8 M
PO4-3 = 1.778x10-8 M
Now we have the value of both of the product, we will express it
intonthe Ksp formula.

Ksp= (Ba+2)³ x (PO4-3)2

Ksp= (2.667x10-8 )³ x (1.778 x 10-8 )²
Ksp= 6x10-39 is the solubility product constant of Ba3(PO4)2
 MOLAR SOLUBILITY
What if the given is the Ksp, and you need to find
the Molar Solubility?
Ex 3) the Ksp Of Ca(OH)2 is 1.3 x 10^-6. Find the Molar solubility
of Ca(OH)2.
First step is to express it to chemical equilibrium
Ca(OH)2(s) ⇌ Ca+2(aq) + 2OH- (aq)
Then we will use the ICE method.

Ca(OH)2(s) Ca+2(aq) 2OH- (aq)

Initial none 0 0

Change none +x +2x

Equilibrium none x 2x
 MOLAR SOLUBILITY
What if the given is the Ksp, and you need to find
the Molar Solubility?
Ex 3) the Ksp Of Ca(OH)2 is 1.3 x 10^-6. Find the Molar solubility
of Ca(OH)2.

First step is to express it to chemical equilibrium

Ca(OH)2(s) ⇌ Ca+2(aq) + 2OH- (aq)
Then we will use the ICE method.

Ca(OH)2(s) Ca+2(aq) 2OH- (aq)

Initial none 0 0

Change none +x +2x

Equilibrium none x 2x
 MOLAR SOLUBILITY
What if the given is the Ksp, and you need to find
the Molar Solubility?
After getting the value of ICE. We will proceed by using the Ksp
formula in finding the Molar Solubility.
Ksp = (Ca+2) x (OH-)²
Using the value of the C (change) in our product, we input it inside the
open and close parenthesis. The exponent outside is base on the
coefficient of the product:

Ksp= (x) x (2x)²

Then we multiply it with the accordance of the rule of adding exponent.
Ksp= (x) x (4x²)
Ksp= 4x³
 MOLAR SOLUBILITY
What if the given is the Ksp, and you need to find
the Molar Solubility?
Now, we will do this…
1.3 x 10^-6 = 4x³
4 4
3.25x10-7 = x³
We will do this, to remove the x³
³√3.25 x 10^-7 = ³√x³
³√3.25 x 10^-7 = x
You can solve the ³√3.25 x 10-7 but I suggest you do this instead.
(3.25x10-7)1/3 or 0.33333
Then you will get the result.
6.87x10-3 is the Molar solubility of Ca(OH)2.
 COMMON ION EFFECT
The common ion effect describes the effect on equilibrium
that occurs when a common ion (an ion that is already contained in
the solution) is added to a solution. The common ion effect generally
decreases solubility of a solute.
It applies to the Chatelier's Principle, wherein it describes the
behavior of a equilibrium. Increasing of the solution will shift the
equilibrium.
Example is:
AgI (s) ⇌ Ag+ (aq) + I- (aq)
We can put KI in a solution of AgI, they both contain a common Ion which is “I-
“. Therefore the equilibrium will shift to the left, because it will use the excess
Iodine anion. More AgI precipitate will form.
 COMMON ION EFFECT
Now lets see it in a quantitative form.
Ca3(PO4)2 has a Ksp value of 2.0 x 10-29.
What is its solubility in 0.1 M of H3PO4

Lets first express it in a into a chemical equilibrium

Ca3(PO4)2 (s) ⇌ 3Ca+2 (aq) + 2PO4-3 (aq)
Then we will use the ICE method

Ca3(PO4)2 (s) 3Ca+2 (aq) 2PO4-3 (aq)

Initial none 0 0.1

Change none +3x +2x

Equilibrium none 3x 2x + 0.1

 COMMON ION EFFECT
Above the table, you notice we put O.1 in the Initial and Change.
Since we add 0.1 M of H3PO4 solution in the Ca3(PO4)2, there is a common Ion present in them, it is the
PO4-3. That's why we put it in the Initial. Whilst in the equilibrium column we add 0 1 because it is a
quantitative Mole added with the 2Mol of 2PO4-3.
Then the next step is the Ksp equation
Ksp = (Ca+2)³ x (PO4-3)²
2.0 x 10^-29 = (3x)³ (0.1 + 2x)2

However, in the next step, we will eliminate 2x, because 2.0 x 10^-29 is every small number, we can
assume it doesn't exist or play a role, so only 0.1 will be left in the equation.
2.0 x 10-29 = (3x)³ x (0.1)²
2.0 x 10-29 = 0.27x³
0.27 0.27
³√7.4 x 10 -29 = ³√x3
-29 1/3
(7.4 x 10 ) or 0.3333 = x
4.2 x 10-10 = x Is the Solution Mol/L of Ca3(PO4)2 if you start with 0.1 M/L of H3PO4 originally.
Solubility
Equilibrium
• pH and Solubility
• Complex ion Equilibrium and
Solubility
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CHEMISTRY & YOU

pH and Solubility
• pH is a measurement of the acidity and basicity
The range goes from 0 to 14, with 7 being
neutral. pHs of less than 7 indicate acidity,
whereas a pH of greater than 7 indicates a base.
• Solubility is the maximum amount of a substance
that will dissolve in a given amount of solvent.
• for a solution to have a pH, it has to be aqueous
(contains water).
 CHEMISTRY & YOU

pH and Solubility
• Weakly soluble ionic compounds have solubilities
which depend on the pH of the solution.
• Hydroxides - the OH- ion is directly involved in the
equilibrium constant.

Example
Zinc hydroxide Zn(OH)2 has Ksp = 4.5×10-17
In pure water:
Express it to chemical equilibrium
Zn(OH)2 (aq) Zn2+ (aq) + 2OH- (aq)
 CHEMISTRY & YOU

pH and Solubility
Use the ICE table method
Zn(OH)2 (aq) Zn2+ (aq) 2OH- (aq)
I 0 0

C +x +2x

E x 2x

Zn(OH)2 (s) ß à Zn2+ (aq) + 2OH- (aq)

Ksp = 4.5×10-17 = x(2x)2.
x = (4.5×10-17 )/4]1/3 = 2.2×10-6 M.
The resulting pH is [OH-] = 2x = 4.4×10-6 M therefore
pH = 14 - pOH
= 14 - (-log( 4.4×10-6))
= 8.64
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CHEMISTRY & YOU

pH and Solubility
● LP states if we stress the system (by changing the pH)
then the equilibrium will shift to reduce the stress.

● If pH < 8.64 (more acidic) then [OH-] decreases (rx shifts

right to try to produce more). Solubility increases.

● If pH > 8.64 (more basic) then [OH-] increases (rx shifts

left to try to use more). Solubility decreases.
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CHEMISTRY & YOU

pH and Solubility
• Now what will happen in this example is we
start again but this time, we try to dissolve the
zinc hydroxide into a solution buffered at pH =
6.0.

[OH-] = antilog[ -(14 – pH)]

= antilog[ -(14 – 6)] = 1.0×10-8.
Ksp = [Zn2+][OH-]2 [Zn2+]
= Ksp/[OH-]2= 4.5×10-17/(1.0×10-8)2
= 0.45 M
Much larger solubility than than in pure water.
 CHEMISTRY & YOU

Complex ion Equilibrium and Solubility

• Comprised of two important parts: the Central atom and it’s
sorounding Ligands.
• Central atom can be any metallic ion (usually a transition
metal).
• Ligands molecules or ion having lone-pair of electrons
which can be ‘donated’ to a metal ion to form a covalent
bond.
• Common Ligands includes H2O, NH3, Cl-, CN_.

Example:
Complex ion Equilibrium and Solubility >>
Formation Constant

Coordination Central
Examples Ligands
Number Atom

2 Ag(NH3)2+ (NH3)2 Ag

Cu(NH3)42+

CO(H2O)62+
Complex ion Equilibrium and Solubility >>
Formation Constant
● Complex ion Equilibria have their own unique Equilibrium constant that is
called Formation Constant (Kf).
• Describes the formation of a complex ion from its central ion and attached
ligands. This constant may be called stability or association constant.
• Common metal/ligand Kf values are tabulated
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Complex ion Equilibrium and Solubility >>

Formation Constant
● Tabulated formation Constant
Complex ion Equilibrium and Solubility >>
Formation Constant
• The equation for formation constant (Kf):

•M- metal ion

•L- ligands
•x and y- coefficients
Example: the formation reaction of the Silver Cyanide (l)
complex ion
 Complex ion Equilibrium and Solubility
> Dissociation constant (Kd)

• Due to how large formation constants often are it is not uncommon to see
them listed as logarithms in the form log Kf. You may also see them in the form
of a dissociation constant, (Kd)
• The dissociation constant (Kd) is the reciprocal, or inverse value of Kf that is
described as the instability of a complex ion.
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Complex ion Equilibrium and Solubility

In logarithm form Kf and Kd would be:

● Log Kf = log (5.6 x 1018) = 18.7

● Log Kf = log (1.8 x 10 ) = _18.7
-19
 Complex ion Equilibrium and Solubility>
Calculating Stepwise Formation Constant

1 The formation constant for Ag(NH3)^+ and Ag(NH3)2^+ are 2.1 x

10^3 and 8.2 x 10^3.
a.) Write the equations for the Stepwise Formation of Ag[NH3]+
and Ag[NH3]2+
b.) Calculate the value for the overall formation constant of
Ag[NH3]2+.
 Complex ion Equilibrium and Solubility>
Calculating Stepwise Formation Constant

The formation constant for Ag(NH3)^+ and Ag(NH3)2^+ are 2.1

x 10^3 and 8.2 x 10^3.
a.) Write the equations for the Stepwise Formation of Ag[NH3]+
and Ag[NH3]2+
b.) Calculate the value for the overall formation constant of
Ag[NH3]2+.
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Complex ion Equilibrium and Solubility

●Theformation of a complex ion by adding a
complexing agent increases the solubility of a
compound product.
Application of the
Solubility Product
Principle to
Qualitative
Analysis
 QUALITATIVE ANALYSIS
Qualitative analysis is the
determination of the types of ions present
in a solution. There are some 20 common
cations that can be analyzed readily in
aqueous solution. These cations can be
divided into five groups.
 QUALITATIVE ANALYSIS
Group 1. Insoluble chlorides:
When HCl is added to a mixture of
cations,
therefore, only AgCl, Hg2Cl2, and PbCl2
precipitate, leaving the other cations in
solution.
 QUALITATIVE ANALYSIS
Group 2. Acid-insoluble sulfides:
After any insoluble chlorides have been removed, the
remaining solution, now acidic from HCl treatment, is
treated with H2S. Since H2S is a
weak acid compared to HCl, its role here is to act as a
source for small amounts of sulfide. Only the most
insoluble metal sulfides—CuS, Bi2S3, CdS, PbS, HgS,
As2S3, Sb2S3,and SnS2 precipitate.
 QUALITATIVE ANALYSIS
Group 3. Base-insoluble sulfides and
hydroxides:
After the solution is filtered to remove any acid-insoluble
sulfides, it is made slightly basic, and (NH4)2S is added.The
ion products for many of the more soluble sulfides exceed
their Ksp values and thus precipitation occurs. The metal
ions precipitated at this stage are Al3+(aq), Cr3+(aq),
Fe3+(aq), Zn2+(aq), Ni2+(aq), Co2+(aq), and Mn2+(aq). (The
Al3+(aq), Fe3+(aq) and Cr3+(aq) ions do not form insoluble
sulfides; instead, they precipitate as insoluble hydroxides.)
 QUALITATIVE ANALYSIS
Group 4. Insoluble phosphates:
At this point, the solution contains only metal ions from
groups 1A and 2A of the periodic table. Adding
(NH4)2HPO4 to a basic solution precipitates the group
2A elements Mg2+(aq), Ca2+(aq), Sr2+(aq), and
Ba2+(aq) because these metals form insoluble
phosphates.
 QUALITATIVE ANALYSIS
Group 5. The alkali metal ions and
NH4+(aq):
At this stage, the only cations possibly remaining in
solution are Na+, K+, and NH+4
The ions that remain after removing the insoluble
phosphates are tested for individually. A flame test
can be used to determine the presence of K+(aq), for
example, because the flame turns a characteristic
violet color if K+(aq) is present
QUALITATIVE ANALYSIS
QUALITATIVE ANALYSIS