Lecture-9

Solubility Product & pH

Text
Essentials of Physical Chemistry
By Bahl & Tuli
 What is solubility product law?

The product of concentrations of ions arising out

of a sparingly (weakly soluble) salt in a saturated
solution at any constant temperature is a constant.

For example, lead sulphate is a sparingly

soluble electrolyte.

PbSO4 → Pb+2 + SO4-2

(solid) (in solution)

Sep 18, 2022 Solubility Product & pH 2

 Solubility Product (contd.)

According to the solubility product law,

[Pb+2] [SO4-2] = a constant

where [Pb+2] = concentration of Pb+2 ions as gram
ions per liter and [SO4-2] = concentration of SO 4-2
ions as gram ions per liter.

Example-1: The solubility of PbSO4 in H2O at

250C is found to be 0.0037 gm/100gm H2O. Find
its solubility product (Ksp) at that temperature.

Sep 18, 2022 Solubility Product & pH 3

 Solution:
The molecular weight of PbSO4 = 303.37
The solubility of PbSO4 = 0.0037g/100g of H2O
= 0.0037g/100ml of H2O
= 0.037g/1000ml of H2O
= 0.037 g/liter
 = 0.037303.37 mole/liter
= 1.2  10-4 mole/liter.
Since PbSO4 dissociates completely in H2O, each
molecule of it on dissociation produces,
1.2  10-4 moles Pb+2 ions/liter
1.2  10-4 moles SO4-2 ions/liter
 Ksp = [Pb+2] [SO4-2] = (1.2  10-4)(1.2  10-4)
= (1.44  10-8) Ans.
Sep 18, 2022 Solubility Product & pH 4
Problem 2. The solubility product of CuCl 2 is 3.2  10-7
at 250C. Calculate the solubility of CuCl 2 in mole litre-1.

⚫ CuCl2 is a sparingly soluble salt.

⚫ Let x is the solubility of CuCl2 in mole litre-1
⚫ The following equilibrium exists in its saturated solution:
⚫ CuCl2 ↔ Cu+2 + 2Cl-
⚫ Equilibrium concentration, x x 2x
⚫ Therefore, solubility product, Ksp = [Cu+2 ] [Cl-]2
⚫ or, 3.2  10-7 = [x] [2x]2
⚫ or, 4x3 = 3.2  10-7
⚫  x = 4.3 x 10-3 mole litre-1
⚫ Ans

Sep 18, 2022 Solubility Product & pH 5

Problem 3. Ksp of CaF2 is 1.7  10-10 and its mol. wt. is
78 g mole-1. What volume of the saturated solution will
contain 0.078 g of CaF 2?
⚫ CaF2 is a sparingly soluble salt.
⚫ Let x is the solubility of CaF 2 in mole litre-1
⚫ The following equilibrium exists in its saturated solution:
⚫ CaF2 ↔ Ca+2 + 2F-
⚫ Equilibrium concentration, x x 2x
⚫ Therefore, solubility product, Ksp = [Ca+2 ] [F-]2
⚫ or, 1.7  10-10 = [x] [2x]2
⚫ or, 4x3 = 1.7  10-10
⚫  x = 3.5 x 10-4 mole litre-1
⚫  1 litre saturated solution contains 3.5 x 10-4 mole of CaF2

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Sep 18, 2022 Solubility Product & pH 7
 ……Problem-3 (contd.)

⚫ No. moles of CaF2 = 0.078g / (78g/mole)

⚫ = 1.0 x 10-3 moles

1litre 1.0 10−3 mole

⚫  Volume of the solution =
3.5 10−4 mole

⚫ = 2.857 litre
⚫ Thus, 0.078 g of CaF2 is contained in 2.9 litres of the
saturated solution. Ans

Sep 18, 2022 Solubility Product & pH 8

Sep 18, 2022 Solubility Product & pH 9
 Solubility Product vs Ionic Product

The solubility product of an insoluble substance

is the product of the concentrations of its ions at
equilibrium.

The ionic product is the product of actual

concentrations of ions that may or may not be in
equilibrium with the solid.

Sep 18, 2022 Solubility Product & pH 10

 Solubility Product Principle
⚫ When the ionic product is equal to the
solubility product, the solution is saturated.

⚫ When the ionic product exceeds the solubility

product, the solution is supersaturated and
precipitation will occur.

⚫ When the ionic product is less than the

solubility product, the solution will be
unsaturated.
Sep 18, 2022 Solubility Product & pH 11
 Common-ion effect
The reduction of the degree of dissociation of a
salt by the addition of a common-ion is called the
common-ion effect. For example- NaCl in AgCl
solution.

AgCl (s)  Ag+(aq) + Cl- (aq)

Addition of NaCl shift equilibrium to left due to

excess Cl- ions and decrease solubility of AgCl.

Sep 18, 2022 Solubility Product & pH 12

 Application of
Solubility Product Principle
(1) Purification of common salt.
A saturated solution of common salt freed from suspended
impurities is taken and HCl gas passed through it. The
equilibrium
NaCl  NaCl  Na+ + Cl-
(solid) (dissolved)
On passing HCl gas, the concentration of Cl- ions is increased
because HCl is highly ionized. The ionic product [Na+][Cl-]
thus considerably increases so much so that it exceeds the
solubility product of sodium chloride at the given temperature.
The result is a supersaturated solution of NaCl from which
solid NaCl precipitates out in order to restore the equilibrium.
Sep 18, 2022 Solubility Product & pH 13
Application…(contd)

(2) Salting out of soap

Ordinary soap is a mixture of the sodium salts of higher
fatty acids and is abtained in the form of a concentrated
solution as a result of saponification. From the solution,
soap precipitates out on the addition of a saturated
common salt solution because the concentration of [Na+]
ions increases and the ionic product [Na+][CnH2n+1COO-]
exceeds the solubility product of soap at that
temperature.

Sep 18, 2022 Solubility Product & pH 14

 Saponification
⚫ Saponification is a process that involves
conversion of fat or oil into soap and alcohol by
the action of heat in the presence of aqueous
alkali. Soaps are salts of fatty acids whereas fatty
acids are saturated monocarboxylic acids that have
long carbon chains e.g. CH₃(CH₂)₁₄COOH.

Sep 18, 2022 Solubility Product & pH 15

Sep 18, 2022 Solubility Product & pH 16
Problem 4. Calculate the solubility of AgCl (Ksp = 1.7 
10-10) in 0.01 M NaCl solution.

⚫ AgCl ↔ Ag+ + Cl- NaCl ↔ Na+ + Cl-

equilib. conc. x x x 0.01 0.01 0.01M
⚫ Complete ionization of the salt in aqueous solution is assumed.
Therefore, total concentration of Cl- in the solution =
⚫ 0.01 M (from NaCl) + x M (from AgCl)
⚫ As AgCl is sparingly soluble, x is negligibly small.
⚫  [Cl-]  0.01 M
⚫  Ksp = [Ag+] [Cl-]
⚫ or, 1.7 x 10-10 = (x)(0.01) M
⚫ or, x = 1.7 x 10-8 M
⚫  The solubility of AgCl in 0.01M NaCl solution is 1.7 x 10-8 M Ans

Sep 18, 2022 Solubility Product & pH 17

Sep 18, 2022 Solubility Product & pH 18
Problem 5. Ksp of Mg(OH)2 is 1.8  10-11 at 250C.
Calculate the solubility of Mg(OH) 2 in 0.1 M aqueous
NaOH solution.
⚫ Mg(OH)2 ↔ Mg+2 + 2OH- NaOH ↔ Na+ + OH-
equilib. conc. x x 2x 0.1 0.1 0.1M
⚫ Complete ionization of the salt in aqueous solution is assumed.
Therefore, total concentration of OH- in the solution =
⚫ 0.1 M (from NaOH) + 2x M (from Mg(OH)2)
⚫ As Mg(OH)2 is sparingly soluble, x is negligibly small.
⚫  [OH-] = (0.1 + 2x)M  0.1 M
⚫  Ksp = [Mg+2] [OH-]2
⚫ or, 1.8 x 10-11 = (x)(0.1)2 M
⚫ or, x = 1.8 x 10-9 M
⚫  The solubility of Mg(OH)2 in 0.1M NaOH solution is 1.8 x 10-9M
⚫ Ans

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Sep 18, 2022 Solubility Product & pH 20
Sep 18, 2022 Solubility Product & pH 21
Next Class: Quiz-4

SOLUTION, SOLUBILITY,
SOLUBILITY-PRODUCT
Sep 18, 2022 Solubility Product & pH 22
Ionic Product of Water:
Ionization of Water
Water is known to be slightly ionized,

H2O  H+ + OH-

But H+ ions get hydrated to H3O+ ions by water,

acting as a base. Water act as an acid by losing H+
ion. Thus

H2O + H2O  H3O+ + OH-

Sep 18, 2022 Solubility Product & pH 23

 Ionization of Water (contd.)
Applying law of chemical equilibrium,
[ H + ][OH − ] [ H 3 O + ][OH − ]
K= , or K=
[ H 2 O] [ H 2 O][ H 2 O]

In case of dilute solution,

K [H2O] = [H+] [OH-], or K [H2O]2 = [H3O+] [OH-]

Since the ionic concentrations are very small, the

concentration of unionized water may be taken as constant,
thus
K [H2O] = Kw, or K [H2O]2 = Kw
Sep 18, 2022 Solubility Product & pH 24
 Ionization of Water (contd.)

 Kw = [H+] [OH-] = [H3O+] [OH-]

Kw is known as ionic product of water and

may be defined as the product of concentration of
H+ ions and OH- ions in pure water. It is constant
at constant temperature.

At 250C, the value of Kw is 1  10-14.

Sep 18, 2022 Solubility Product & pH 25

 Ionization of Water (contd.)
In case of pure water and also in the case of
neutral solutions, the molar concentration of H+
ions and OH- ions are equal.

[H+] = [OH-] = (1  10-14) = 1  10-7 moles/litre

For neutral solution [H+] = [OH-] = (1  10-14) = 1  10-7

moles/litre.
For acidic solution [H+]  1  10-7 > [OH-] moles/litre.
For basic solution [OH-]  1  10-7 > [H+] moles/litre.

Sep 18, 2022 Solubility Product & pH 26

pH value:
The acidity or the basicity of a solution can be
expressed in terms of hydrogen ion concentration.

Kw 110 −14 K w 110 −14

[H+] = = and [OH-] = =
[OH ] [OH − ]
− +
[H ] [H + ]

pH of a solution is the negative logarithm of

hydrogen ion concentration (called pH scale,
Sorensen in 1909).

Sep 18, 2022 Solubility Product & pH 27

pH value (contd.)
+ 1
pH = − log10 [ H ] = log10 +
[H ]
− 1
pOH = − log10 [OH ] = log10
[OH − ]

For pure water, [H+] = [OH-] = 1  10-7 moles/litre

 pH = − log10 [1 10 −7 ] = − (−7) = 7
 pOH = − log10 [1 10 −7 ] = − (−7) = 7

 pH + pOH = 7 + 7 = 14

Sep 18, 2022 Solubility Product & pH 28

Example-2:
# Calculate the pH of 0.001 M HCl.

Solution:
HCl is a strong acid and it is completely dissociated in
aqueous solution.

HCl  H+ + Cl-
0.001 M 0.001 M

For every molecule of HCl, there is one H+, therefore

[H+] = [HCl]

Sep 18, 2022 Solubility Product & pH 29

 Solution (contd)
or [H+] = 0.001 M

 pH = -log (0.001)

= -log (1  10-3)

= - log 1 + 3 log 10

= 3

Therefore the pH of 0.001 M HCl is 3. Ans.

Sep 18, 2022 Solubility Product & pH 30

Sep 18, 2022 Solubility Product & pH
Problem 6. Calculate pH and pOH of 0.02 M
H2SO4 solution. Kw = 1  10-14 at 250C.
⚫ H2SO4 ↔ 2H+ + SO4-
⚫ equilib. conc. 1M 2M 1M

(2H3O+)
If H2SO4 in 1M solution ionizes
completely, [H3O+] will be 2M.
⚫ Therefore, in a 0.02 M H2SO4 solution
⚫ [H3O+] = 0.04 M
⚫  [OH-] = Kw / [H3O+] = (1  10-14 )/ 0.04 = 2.5  10-13 M
⚫  pH = -log [H3O+] = -log (0.04) = 1.40
⚫  pOH = -log [OH-] = -log (2.5  10-13) = 12.60 Ans.
Sep 18, 2022 Solubility Product & pH 32
Problem -7. pH of an aqueous solution of HCl is
2.699 at 250C. Calculate the molarity of the solution.

⚫ We know from the definition of pH,

1
pH = − log10 [ H + ] = log10
⚫ [H + ]
⚫  2.699 = -log [H3O+]
⚫ or, [H3O+] = antilog (- 2.699) = 0.002 M
⚫ As HCl is a strong acid, it will ionize completely in the
aqueous solution. So the molarity of HCl in the
solution will be equal to the concentration of H3O+.
⚫  Molarity of HCl in the solution is 0.002. Ans.

Sep 18, 2022 Solubility Product & pH 33

 Importance of pH in our daily Life
⚫ Most foods are slightly acidic; our
⚫ All living "bodily fluids" are slightly alkaline, as is
organisms seawater— not surprising, since early
are pH animal life began in the oceans. The pH of
sensitive freshly-distilled water will go downward as
and can it takes up carbon dioxide from the air.
"Acid" rain is by definition more acidic than
survive pure water in equilibrium with atmospheric
only in a CO2, owing mainly to sulfuric and nitric
narrow acids that originate from fossil-fuel
range of emissions of nitrogen oxides and SO2.
pH. ⚫ pH of the soil: Plants require a specific pH
range for their healthy growth.
Sep 18, 2022 Solubility Product & pH 34
Sep 18, 2022 Solubility Product & pH 35
 Importance of pH in our daily Life…
⚫ Plants and animals ⚫ pH in our digestive system:
are pH sensitive: Our It is very interesting to note
body works within the that our stomach produces
pH range of 7.0 to 7.8. hydrochloric acid. It helps in
When pH of rain water the digestion of food without
is less than 5.6, it is harming the stomach. During
called acid rain. When indigestion the stomach
acid rain flows into the produces too much acid and
rivers, it lowers the pH this causes pain and irritation.
of the river water. The To get rid of this pain, people
survival of aquatic life use bases called
in such rivers becomes antacids. These antacids
difficult. neutralise the excess acid.
Sep 18, 2022 Solubility Product & pH 36
 Importance of pH in our daily Life…

⚫ pH change as the cause of tooth decay: Tooth decay

starts when the pH of the mouth is lower than 5.5. Tooth
enamel, made up of calcium phosphate is the hardest
substance in the body. It does not dissolve in water, but is
corroded when the pH in the mouth is below 5.5. Bacteria
present in the mouth produce acids by degradation of sugar
and food particles remaining in the mouth after eating. The
best way to prevent this is to clean the mouth after eating
food. Using toothpastes, which are generally basic, for
cleaning the teeth can neutralize the excess acid and
prevent tooth decay.

Sep 18, 2022 Solubility Product & pH 37

 Importance of pH in our daily Life…
⚫ Self defence by animals ⚫ The balance of pH in our
and plants through body also helps to regulate
chemical warfare: Wasps our breathing rate
(insect) and jellyfish have (carbonic acid in our
an alkaline sting and bees blood), controls
have an acidic sting. So microorganisms on skin,
with wasps stung area can and activates enzymes.
be treated with vinegar, Blood has a pH which
and bees with soap or needs to be maintained
baking soda. Stinging hair between 7.35 and 7.45, or
of nettle (plant) leaves else serious illness and
inject methanoic acid death may occur.
causing burning pain.
Sep 18, 2022 Solubility Product & pH 38
Next Class: Electrochemistry & Battery
Syllabus for Quiz-5
(pH & Problems, Electrochemistry &
Battery)

Thank you