Colligative properties 1

Colligative properties
Colligative properties are properties of solutions that depend on the number of molecules in a given volume of
solvent and not on the properties (e.g. size or mass) of the molecules.[1] Colligative properties include: lowering of
vapor pressure; elevation of boiling point; depression of freezing point and osmotic pressure. Measurements of these
properties for a dilute aqueous solution of a non-ionized solute such as urea or glucose can lead to accurate
determinations of relative molecular masses. Alternatively, measurements for ionized solutes can lead to an
estimation of the percentage of ionization taking place.

Vapor pressure
The relationship between the vapor pressure and concentration is given by Raoult's law, which states that:
The vapor pressure of an ideal solution is dependent on the vapor pressure of each chemical component and
the mole fraction of the component present in the solution.
(For details, see the article on Raoult's law.) Colligative properties are mostly studied for dilute solutions.

Boiling point and freezing point

Both the boiling point elevation and the freezing point depression are proportional to the lowering of vapor pressure
in a dilute solution

Boiling point elevation

Boiling Pointtotal = Boiling Pointsolvent + ΔTb
where
ΔTb = molality * Kb * i, (Kb = ebullioscopic constant, which is 0.51°C kg/mol for the boiling point of water; i
= Van 't Hoff factor)
Boiling point is achieved in the establishment of equilibrium between liquid and gas phase. At the boiling point, the
number of gas molecules condensing to liquid equals the number of liquid molecules evaporating to gas. Adding any
solute effectively dilutes the concentration of the liquid molecules, slowing the liquid to gas portion of this
equilibrium. To compensate for this and re-attain the equilibrium, boiling point is achieved at higher temperature.
Any description of a colligative property which includes steric occlusion, or blocking of the surface to reduce the
vapor pressure has no basis in reality, even despite this explanation being frequently taught. This is also why vapor
pressure and boiling point are independent of a liquid's accessible surface area. Alternatively, measurements for
ionized solutes can lead to an estimation of the percentage of ionization taking place.

Freezing point depression

Freezing Pointsolution = Freezing Pointsolvent - ΔTf
where
ΔTf = molality * Kf * i, (Kf = cryoscopic constant, which is 1.86°C kg/mol for the freezing point of water,; i =
Van 't Hoff factor)
Freezing point, or the equilibrium between a liquid and solid phase is generally lowered in the presence of a solute
compared to a pure solvent. The solute particles cannot enter the solid phase, hence, fewer molecules participate in
the equilibrium. Again, re-establishment of equilibrium is achieved at a lower temperature at which the rate of
freezing becomes equal to the rate of liquefying.
Colligative properties 2

Osmotic pressure
Two laws governing the osmotic pressure of a dilute solution were discovered by the German botanist W. F. P.
Pfeffer and the Dutch chemist J. H. van’t Hoff:
1. The osmotic pressure of a dilute solution at constant temperature is directly proportional to its concentration.
2. The osmotic pressure of a solution is directly proportional to its absolute temperature.
These are analogous to Boyle's law and Charles's Law for gases. Similarly, the combined ideal gas law, PV = nRT,
has an analog for ideal solutions:
πV = nRTi
where: π = osmotic pressure; V is the volume; T is absolute temperature; n is the number of moles of solute; R =
8.3145 J K-1 mol-1, the molar gas constant; i = Van 't Hoff factor.

References
[1] W.J. Moore Physical Chemistry Prentice-Hall 1972
Article Sources and Contributors 3

Article Sources and Contributors

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