SOLUBILITY AND HENRY’S LAW

SOLUBILITY(S):

Definition: It is the maximum amount of solute that can be dissolved in a given amount of solvent at a given
temperature.
[Note: Relation between solubility(S) and solubility product(𝐾𝑠𝑝 )]

• Molecules of single elements are non-polar (e.g.: H2, O2 Cl2 etc)

• If central atoms don’t have lone pair and all the adjacent atoms are same, then compound is non-polar.
• If central atom contains only one lone pair the compound is polar.

• Heteronuclear diatomic molecules are always polar.

• Solubility in water increases with increase in polarity (dipole moment). Polar molecules and ionic
compounds are most soluble in water. Non-polar compounds like hydrocarbons are not soluble in water.
• Solubility in non-polar solvent (n-Octane, Benzene etc) decreases with increase in polarity.
Ionic< polar< non-polar

Non-polar+ Non-polar London dispersion force

Non-polar + Polar Dipoles induce dipole interactions
Polar + Polar Dipole – Dipole interaction
Polar + Ionic Ion- Dipole interaction
Ionic + Ionic Electrostatic force

Factors affecting SOLUBILITY

a. Nature of solute and solvent
Solute-solute interactions and solvent-solvent interactions are almost same as solute-solvent interactions
b. Temperature
 c. Pressure
Solubility of gas increases with increase in partial pressure of the gas
(With increase in pressure number of gas molecule per unit volume increases and hence rate at which gas
molecules striking the surface increases.)

HENRY’S LAW
The solubility of a gas in a liquid is directly proportional to the partial pressure of the gas present above the
surface of liquid or solution.
OR
The partial pressure of the gas in vapour phase (𝑃𝑔𝑎𝑠 ) is proportional to the mole fraction of the gas (𝑋𝑔𝑎𝑠 ) in the
solution”

𝑃𝑔𝑎𝑠 ∝ 𝑋𝑔𝑎𝑠

𝑛𝑔𝑎𝑠 𝑛𝑔𝑎𝑠
𝑋𝑔𝑎𝑠 = ≈ 𝑤1 and 𝑤2are the amount of gas dissolved
𝑛𝑔𝑎𝑠 + 𝑛𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑛𝑠𝑜𝑙𝑣𝑒𝑛𝑡 when pressures are 𝑝1 and 𝑝2 respectively

𝐾𝐻 ∝ Temperature
1
Solubility ∝ 𝐾𝐻

APPLICATION OF HENRY’S LAW

1. In soft drink/soda water CO2 is passed through high pressure. Because at high pressure the solubility of CO2 is
more.
2. Scuba divers go deep into the sea which result in high pressure under water, which cause more solubility of gases
inhaled. When diver come to surface the pressure decreases and this release the dissolve gases and lead to the
formation of bubble of 𝐍𝟐 in blood. This blocks the capillaries and create a condition called Bent.
3. At high altitude partial pressure of O2 is less than that of ground. This leads to low concentration of O 2 in blood
and tissue of the people. This leads to weakness and inability to think properly for a climber. This system is called
Anoxia.
VAPOUR PRESSURE AND RAOULT’S LAW
Definition: Under equilibrium conditions the pressure exerted by the vapours of the liquid over the liquid phase
is called vapour pressure.
✓ When a non-volatile solute is added to a volatile solvent vapour pressure of the solution decreases. This is
because the fraction of surface occupied by the volatile component decreases.

Factors affecting vapour pressure

a. V.P ∝ 𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒
1
b. V.P. ∝ 𝐵𝑜𝑖𝑙𝑖𝑛𝑔 𝑃𝑜𝑖𝑛𝑡

Raoult’s Law

General form: For any solution the partial vapour pressure of each volatile component in the solution is directly
proportional to its mole fraction.

𝑃𝐴 = 𝑃𝐴0 × 𝑋𝐴

Case: I (Non-volatile solute is dissolved in a volatile solvent)

The partial vapour pressure of the solution is directly proportional to its mole fraction of volatile component.
0
𝑃𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 𝑃𝑠𝑜𝑙𝑣𝑒𝑛𝑡 × 𝑋𝑠𝑜𝑙𝑣𝑒𝑛𝑡

Case: II (When two volatile liquids are mixed with each other)
For a solution of volatile liquids, the partial vapour pressure of each component of the solution is directly
proportional to its mole fraction present in solution.
 Total V.P. 𝑃𝑇𝑜𝑡𝑎𝑙 = 𝑃𝐴 + 𝑃𝐵

= 𝑃𝐴0 𝑋𝐴 + 𝑃𝐵0 𝑋𝐵

=𝑃𝐴0 + (𝑃𝐵0 − 𝑃𝐴0 ) 𝑋𝐵

𝑋𝐴 and 𝑋𝐵 are the mole fraction of liquids in solution

Mole fraction of liquid in vapour phase:

𝑃𝐴 𝑃𝐴
𝑌𝐴 = =
𝑃𝑇𝑜𝑡𝑎𝑙 𝑃𝐴 + 𝑃𝐵
𝑃𝐵 𝑃𝐵
𝑌𝐵 = =
𝑃𝑇𝑜𝑡𝑎𝑙 𝑃𝐴 + 𝑃𝐵

IDEAL AND NON-IDEAL SOLUTIONS

IDEAL SOLUTIONS NON-IDEAL SOLUTION
The solutions which obey Raoult’s These solutions don’t obey Raoult’s law.
law exactly at all range of Negative deviation from Raoult’s Positive deviation from Raoult’s
concentration and temperature Law Law
are called ideal solution
Conditions:
A-A, B-B & A-B interactions are A-A & B-B interactions < A-B A-A & B-B interactions > A-B
same interaction interaction
Characteristics:

Observed V.P. = Calculated V.P. Observed V.P. < Calculated V.P. Observed V.P. > Calculated V.P.
𝑃𝐴 = 𝑃𝐴0 × 𝑋𝐴 𝑃𝐴 < 𝑃𝐴0 × 𝑋𝐴 𝑃𝐴 > 𝑃𝐴0 × 𝑋𝐴

∆𝑚𝑖𝑥 𝐻 = 0 ∆𝑚𝑖𝑥 𝐻 = −𝑣𝑒 ∆𝑚𝑖𝑥 𝐻 = +𝑣𝑒

Temperature of the solution Temperature of the solution Temperature of the solution
remain constant increases decreases
∆𝑚𝑖𝑥 𝑉 = 0 ∆𝑚𝑖𝑥 𝑉 = −𝑣𝑒 ∆𝑚𝑖𝑥 𝑉 = +𝑣𝑒
∆𝐺 = −𝑣𝑒 ∆𝐺 = −𝑣𝑒 ∆𝐺 = −𝑣𝑒
∆𝑆 = +𝑣𝑒 ∆𝑆 = +𝑣𝑒 ∆𝑆 = +𝑣𝑒
Examples:

a. n-Hexane and n-Heptane a. Phenol and Aniline a. Ethanol and Acetone

b. Chloroform and Acetone
 b. Bromomethane and c. Chloroform and Benzene b. Carbon disulphide and
Chloromethane d. Nitric acid and Water Acetone
c. Benzene and Toluene c. Benzene ana Acetone
d. Benzene and Carbon
tetrachloride

AZEOTROPES
Binary liquid solutions having the same composition in liquid and vapour phase and boil at a constant
temperature are called Azeotropes/ Azeotropic mixture/ Constant boiling mixture.
✓ Azeotropes are formed by non-ideal solutions.
✓ They can’t be separated by Fractional distillation method.
a. Maximum boiling azeotropes:
✓ Solution showing large negative deviation from Raoult’s law show maximum boiling azeotropes.
✓ B.P. of the mixture is greater than the B.P. of both the component.
✓ HNO3(68% by mass) aqueous solution
b. Minimum boiling azeotropes:
✓ Solution showing large positive deviation from Raoult’s law show minimum boiling azeotropes.
✓ B.P. of the mixture is less than the B.P. of both the component.
✓ Ethanol (95% by volume) aqueous solution

COLLIGATIVE PROPERTIES
The properties of the solutions which depends upon the relative number of solute particles irrespective of
their nature.
Vant’ Hoff factor(i)
𝑇𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠 𝑎𝑓𝑡𝑒𝑟 𝑎𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛/𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛
i= 𝑇𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠 𝑏𝑒𝑓𝑜𝑟𝑒 𝑎𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛/𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛

𝑂𝑏𝑠𝑒𝑟𝑣𝑒𝑑 𝑐𝑜𝑙𝑙𝑖𝑔𝑎𝑡𝑖𝑣𝑒 𝑝𝑟𝑜𝑝𝑒𝑟𝑡𝑖𝑒𝑠

i=
𝐶𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑒𝑑 𝑐𝑜𝑙𝑙𝑖𝑔𝑎𝑡𝑖𝑣𝑒 𝑝𝑟𝑜𝑝𝑒𝑟𝑡𝑖𝑒𝑠

𝑁𝑜𝑟𝑚𝑎𝑙 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠

i=
𝐴𝑏𝑛𝑜𝑟𝑚𝑎𝑙 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠

✓ Vant’ Hoff factor (i) for non-electrolyte (eg. Glucose, Sucrose, Urea etc.) =1
✓ Vant’ Hoff factor (i) for strong electrolyte is equal to the number of ions produce
after dissociation.
✓ Vant’ Hoff factor (i) for weak electrolyte:
For dissociation: i= 1−∝ +𝑛 ∝
∝ = degree of dissociation
𝑛 = 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠 𝑝𝑟𝑜𝑑𝑢𝑐𝑒 𝑎𝑓𝑡𝑒𝑟 𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛
𝛽
For association: i= 1−𝛽 + 𝑛
𝛽 = degree of Association
𝑛 = 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠 𝑎𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑒𝑑
Types of colligative properties

1. Relative lowering in vapour pressure (RLVP)

𝑃 0 −𝑃𝑠 𝑛
RLVP = = 𝑖 𝑋𝑠𝑜𝑙𝑢𝑡𝑒 ≈ 𝑖 𝑛 𝑠𝑜𝑙𝑢𝑡𝑒
𝑃0 𝑠𝑜𝑙𝑣𝑒𝑛𝑡

𝑊𝑠𝑜𝑙𝑢𝑡𝑒 ×1000
2. Elevation of boiling point (∆𝑇𝑏 ) = 𝑖𝐾𝑏 𝑚 = 𝑖𝐾𝑏 𝑀
𝑠𝑜𝑙𝑢𝑡𝑒 ×𝑊𝑠𝑜𝑙𝑣𝑒𝑛𝑡

𝑊𝑠𝑜𝑙𝑢𝑡𝑒 ×1000
3. Depression in freezing point (∆𝑇𝑓 ) = 𝑖𝐾𝑓 𝑚 = 𝑖𝐾𝑓
𝑀𝑠𝑜𝑙𝑢𝑡𝑒 ×𝑊𝑠𝑜𝑙𝑣𝑒𝑛𝑡

𝑊𝑠𝑜𝑙𝑢𝑡𝑒 ×1000×𝑅×𝑇
4. Osmotic pressure (𝜋) = 𝑖𝐶𝑅𝑇 = 𝑖
𝑀𝑠𝑜𝑙𝑢𝑡𝑒 ×𝑉𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛