Dilute solution: Colligative properties

Lowering of Vapor pressure

Elevation of boiling point

Depression of freezing point

Osmotic pressure

Ref.
1. Principles of Physical Chemistry- Maron and Prutton (M&P)
2. Principles of Physical Chemistry- Huque and Mollah (H&M)
3. Chemistry by R. Chang
4. General Chemistry by Ebbing
 Colligative properties
Dilute solution
Conditions to follow colligative properties Non-electrolyte solute
Non-volatile solute

Solution of non-electrolyte
• the solute dissolved in solvent persist in molecular form
Solution of electrolyte
• the solute dissolved in solvent dissociate into electrically charged ions

Colligative properties are those properties of solution that depend on

the ratio of the number of solute particles to the number of solvent
molecules in a solution, and not on the nature of the chemical species
present
a. Vapor pressure lowering
b. Boiling point elevation
c. freezing point depression H &M and M&P
d. Osmotic pressure
 Lowering of vapor pressure
The lowering of vapor pressure due to the addition of non-electrolyte and non-volatile solute

According to Raoult’s Law

P = PoN1 ; P is the vapor pressure of the solution and Po is that of pure solvent
Lowering of vapor pressure, Po-P = Po-PoN1 = Po (1-N1) = PoN2
N1 is the mole fraction of the solvent and N2 is that of solute (N1+N2=1)

The vapor pressure lowering of solvent depends on the vapor pressure of the solvent and the mole fraction
of the solute
From the equation derived above relative lowering of vapor pressure
(Po-P)/Po = N2
Thus, the relative lowering of vapor pressure of a solvent due to the addition
of non-volatile and non-electrolyte solute is equal to the mole fraction of
the solute
M&P

The molar mass of the solute can be calculated from the equation
derived. where W2 and W1 are mass of solvent and M2 and M1 are the
molar mass of solute, respectively.
 Elevation of boiling point

Po

𝑊2
𝐴𝐵 ∆𝑇𝑏 𝑀
= 0 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ∆𝑇𝑏 = 𝑘 ′ 2
𝐴𝐶 𝑝 − 𝑝 𝑊1
𝑀1
∆𝑇𝑏 = 𝑝𝑜 − 𝑝0 . 𝑁1 𝑘 𝑊2
𝑀1 𝑀
∆𝑇𝑏 = 1 − 𝑁1 𝑝0𝑘 ∆𝑇𝑏 = 𝑘 ′
× 2 × 1000 H&M
1000 𝑊1
∆𝑇𝑏 = 𝑁2 𝑘 ′
∆𝑇𝑏 = 𝑘𝑏 𝑚
 Depression of freezing point H & M

𝐷𝐹 ∆𝑇𝑓 𝑊2
= 0 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑀
𝐴𝐹 𝑝 − 𝑝 ∆𝑇𝑓 = 𝑘 ′ 2
𝑊1
∆𝑇𝑓 = 𝑝𝑜 − 𝑝0 . 𝑁1 𝑘 𝑀1 𝑊2
𝑀1 𝑀
∆𝑇𝑓 = 1 − 𝑁1 𝑝0 𝑘 ∆𝑇𝑓 = 𝑘 ′
× 2 × 1000
1000 𝑊1
∆𝑇𝑓 = 𝑁2 𝑘 ′
∆𝑇𝑓 = 𝑘𝑓 𝑚
 Thermodynamic treatment of boiling point elevation and freezing point depression (M & P 315-324)

The Clausius–Clapeyron relation, in chemical thermodynamics, specifies the temperature dependence of

pressure, most importantly vapor pressure, at a discontinuous phase transition between two phases of matter of a
single constituent.
 Osmotic Pressure
Diffusion: movement of solute particles from higher
to lower concentration

Semipermeable membrane: Certain membranes

allow solvent molecules to pass through them but
not solute molecules, particularly not those of
large molecular mass

Osmosis: is the phenomenon of solvent flow

through a semipermeable membrane to equalize
the solute concentrations on both sides of the
membrane
Salt is applying on raw leather to protect it from rot

Japanese
sashimi
7
Laws of Osmosis (H & M)

1st law
 1/V (T constant)
V = Constant

2nd law
 T (V constant)
V= KT

Third law
Equimolar quantities of different solutes dissolved in such a volumes of solvent as to
give the same volume of solution have the same osmotic pressure at the same
temperature
Combination of first and second law
Determination of molar mass
V= nRT V = (w/M)RT
= (n/V) RT =CRT

Solution of problem: H and M, page 245-247) 8

 Osmotic
pressure

P Image: Ebbing 505

The external pressure that must be applied on the solution side to just prevent the
inflow the solvent through the semi-permiable membrane.

Molecular Mechanism of osmosis through semipermeable (H & M) 242-243

Molecular sieve theory

Membrane solution theory
Vapor pressure theory
Membrane bombardment theory
9
 Desalination and Reverse
Osmosis

Reverse osmosis uses high pressure to

force water from a more concentrated
solution to a less concentrated one
through a semipermeable membrane.

Ref- Raymond Chnag)

10
 Isotonic, hypertonic and hypotonic

Ref,Chang-535
HM-249

A cell in (a) an isotonic solution, (b) a hypotonic solution, and (c) a hypertonic
solution. The cell remains unchanged in (a), swells in (b), and shrinks in (c). (d) From
left to right: a red blood cell in an isotonic solution, in a hypotonic
solution, and in a hypertonic solution. 11
Abnormal molar mass from colligative properties: concept of colligative properties for electrolyte ( H &M

Molecular Association: The experimental values of colligative properties are much lower than those expected
from respective equation.
The molar mass derived from these experimental values are much higher than those expected from molecular
formula.

Molecular dissociation:
The values of colligative properties for the electrolytes are abnormally large.
imperial factor i has been introduced.
𝐶𝑜𝑙𝑙𝑖𝑔𝑎𝑡𝑖𝑣𝑒 𝑝𝑟𝑜𝑝𝑒𝑟𝑡𝑖𝑒𝑠𝑂𝑏𝑠𝑒𝑟𝑣𝑒𝑑
𝑣𝑎𝑛′ 𝑡 𝐻𝑜𝑓𝑓 𝐹𝑎𝑐𝑡𝑜𝑟, 𝑖 =
𝐶𝑜𝑙𝑙𝑖𝑔𝑎𝑡𝑖𝑣𝑒 𝑝𝑟𝑜𝑝𝑒𝑟𝑡𝑖𝑒𝑠𝑡ℎ𝑒𝑜𝑟𝑖𝑡𝑖𝑐𝑎𝑙

Arrhenius theory of electrolytic dissociation (M& P) 333-335

14
 Mathematical problems and
solutions

Raymond Chang: 12.7-12.11

Ebbing: 12.9-12.13
Huque and Mollah: All solved problem

15