What are Colligative Properties?

A we have discussed, solutions have different properties than either the solutes or the solvent used to make the solution. Those properties can be divided into two main groups--colligative and non-colligative properties. Colligative properties depend only on the number of dissolved particles in solution and not on their identity. Non-colligative properties depend on the identity of the dissolved species and the solvent.

To explain the difference between the two sets of solution properties, we will compare the properties of a 1.0 M aqueous sugar solution to a 0.5 M solution of table salt (NaCl) in water. Despite the concentration of sodium chloride being half of the sucrose concentration, both solutions have precisely the same number of dissolved particles because each sodium chloride unit creates two particles upon dissolution--a sodium ion, Na+, and a chloride ion, Cl-. Therefore, any difference in the properties of those two solutions is due to a non-colligative property. Both solutions have the same freezing point, boiling point, vapor pressure, and osmotic pressure because those colligative properties of a solution only depend on the number of dissolved particles. The taste of the two solutions, however, is markedly different. The sugar solution is sweet and the salt solution tastes salty. Therefore, the taste of the solution is not a colligative property. Another non-colligative property is the color of a solution. A 0.5 M solution of CuSO4 is bright blue in contrast to the colorless salt and sugar solutions. Other non-colligative properties include viscosity, surface tension, and solubility.

Raoult's Law and Vapor Pressure Lowering

When a nonvolatile solute is added to a liquid to form a solution, the vapor pressure above that solution decreases. 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 will equal the rate of capture to establish a constant, equilibrium vapor pressure above the pure liquid.

If we add a nonvolatile solute to that liquid, the amount of surface area available for the escaping solvent molecules is reduced because some of that area is occupied by solute particles. Therefore, the solvent molecules will have a lower probability to escape the solution than the pure solvent. That fact is reflected in the lower vapor pressure for a solution relative to the pure solvent. That statement is only true if the solvent is nonvolatile. If the solute has its own vapor pressure, then the vapor pressure of the solution may be greater than the vapor pressure of the solvent.

Note that we did not need to identify the nature of the solvent or the solute (except for its lack of volatility) to derive that the vapor pressure should be lower for a solution relative to the pure solvent. That is what makes vapor pressure lowering a colligative property--it only depends on the number of dissolved solute particles.

summarizes our discussion so far. On the surface of the pure solvent (shown on the left) there are more solvent molecules at the surface than in the right-hand solution flask. Therefore, it is more likely that solvent molecules escape into the gas phase on the left than on the right. Therefore, the solution should have a lower vapor pressure than the pure solvent.