COLLIGATIVE PROPERTIES OF DILUTE SOLUTIONS

Colligative Properties of Solution What are Colligative properties of a solution...'why

colligative'? Colligative properties are those properties that depend on the concentration of
the solute particles rather than the kind of solute particles. All colligative properties are
related to each other by virtue of their common dependency on the concentration of the
solute molecules. From Greek word collected together They include:
1) Osmotic pressure
2) vapor pressure lowering
3) Boiling point elevation
4) Freezing point depression

1. Osmotic pressure.

The most important colligative property from a pharmaceutical point of view is

referred to as osmotic pressure. The osmotic pressure of a solution is the external
pressure that must be applied to the solution in order to prevent it being diluted by
the entry of solvent via a process known as osmosis.

Osmosis:

If two solutions of different concentrations are separated by a semi-permeable

membrane (only permeable to the solvent) the solvent will move from the solution of
lower solute concentration to that of higher solute concentration.

Osmotic pressure of non electrolytes:

The relationship between osmotic pressure and the concentration of a non-electrolyte is
given for dilute solutions, which may be assumed to exhibit ideal behaviour, by the van't Hoff
equation:
PV=nRT
1) Where V is the volume of solution,
2) n, is the number of moles of solute,
3) T is the absolute temperature and
4) R is the gas constant.

The osmotic pressure of solutions of different non electrolytes is proportional to the

number of molecules in each solution.
The osmotic pressures of two nonelectrolyte solutions of same molal
concentration are identical.

For example, a solution containing 34.2g of sucrose (mol wt. 342) in

1000 g of water has the same osmotic pressure as a solution containing
18.0 g of anhydrous dextrose (mol wt. 180) in 1000 g water.
These solutions are said to be iso-osmotic with each other because they
have identical osmotic pressures.
But this is not true for electrolytes as they ionize therefore the o.p.
number of particles increase

Osmotic pressure of electrolytes:

If the solute is an electrolyte, the previous equation must be modified to

allow for the effect of ionic dissociation, because this will increase the
number of particles in the solution.
This modification is achieved by insertion of the van't Hoff correction
factor (i) to give:
PV=inRT
Although the above equation may be simpler to remember, the following
form of the equation is more useful.
This form of the equation has been derived by realizing that n/V gives the
concentration of the solute in units of molarity.,
M. P = i M R T
Where the value of i approaches the number of ions produced by the
ionization of the strong electrolytes.
For weak electrolytes (i) represents the total number of particles, ions and
molecules together, in the solution.

2. Vapor pressure lowering:

To understand why that might occur, let's analyze the vaporization process
of the pure solvent then do the same for a solution.
Liquid molecules at the surface of a liquid can escape to the gas phase
when they have a sufficient amount of energy to break free of the liquid's
intermolecular forces. That vaporization process is reversible.
Gaseous molecules coming into contact with the surface of a liquid can be
trapped by intermolecular forces in the liquid.
Eventually the rate of escape (vaporization) will equal the rate of capture
(condensation) to establish a constant, equilibrium vapor pressure above
the pure liquid.
Some of the surface molecules of the solvent are replaced by solute
molecules which do not contribute in the vapor pressure and the surface
area available for the escaping solvent molecules is reduced because
some of that area is occupied by solute particles.
Lowering of Vapour Pressure:
Vapour pressure P1 of solvent over a dilute solution equal to vapour
pressure of pure solvent times the mol fraction of solvent X1
Because the solute non volatile, so the total pressure = the pressure of
the solvent
P = Po - P = Vapour pressure lowering

3. Freezing point depression

The freezing point is depressed due to the vapor pressure lowering
phenomenon.
Freezing point (or melting point): is defined as the temperature at which the
solid and the liquid phases are in equilibrium under a pressure of 1 atm.
The freezing point of pure water is 0C, but that melting point can be
depressed by the adding of a solute such as a salt.
The use of ordinary salt (sodium chloride, NaCl) on icy roads in the winter helps
to melt the ice from the roads by lowering the melting point of the ice.
A solution typically has a measurably lower melting point than the pure
solvent. A 10% salt solution was said to lower the melting point to -6C and a
20% salt solution was said to lower it to -16C
Determination of The freezing point depression: The freezing point depression
Tf is a colligative property of the solution and for dilute solutions is found to
be proportional to the molal concentration cm of the solution: Tf = Kf cm Where
Kf is called the freezing-point-depression constant (cryoscopic constant). A
pleasant application of the freezing point depression is in the making of
homemade ice cream. The ice cream mix is put into a metal container which is
surrounded by crushed ice. Then salt is put on the ice to lower its melting point.
The melting of the solution tends to lower the equilibrium temperature of the
ice/water solution to the melting point of the solution. This gives a temperature
gradient across the metal container into the saltwater-ice solution which is lower
than 0C. The heat transfer out of the ice cream mix allows it to freeze.

4. Boiling Point Elevation

Boiling point elevation is a colligative property related to vapor pressure
lowering. The boiling point is defined as the temperature at which the vapor
pressure of a liquid equals the atmospheric pressure (760 mmHg). Due to vapor
pressure lowering, a solution will require a higher temperature to reach its
boiling point than the pure solvent. The boiling point of pure water is 100C, but
that boiling point can be elevated by the adding of a solute such as a salt. A
solution typically has a measurably higher boiling point than the pure solvent.

Determination of The boiling point elevation:

The boiling point elevation DTb is a colligative property of the solution, and for
dilute solutions is found to be proportional to the molal concentration cm of the
solution: DTb = Kb cm Where Kb is called the boiling-point-elevation
constant(Ebullioscopic constant). Solutions may be produced for the purpose of
raising the boiling point and lowering the freezing point, as in the use of

ethylene glycol in automobile cooling systems. The ethylene glycol (antifreeze)

protects against freezing by lowering the freezing point and permits a higher
operating temperature by raising the boiling point. 4. Freezing point depression.