Freezing Point Depression

As you may have noticed when we looked at the , the freezing point is depressed due to the vapor pressure lowering phenomenon. The points out that fact:

Figure %: Phase Diagram for a Solution and the Pure Solvent Indicating the Freezing Point Depression

In analogy to the boiling point elevation, we can calculate the amount of the freezing point depression with the :

Note that the sign of the change in freezing point is negative because the freezing point of the solution is less than that of the pure solvent. Just as we did for boiling point elevation, we use molality to measure the concentration of the solute because it is temperature independent. Do not forget about the van't Hoff factor, i, in your freezing point calculations.

One way to rationalize the freezing point depression phenomenon without talking about Raoult's law is to consider the freezing process. In order for a liquid to freeze it must achieve a very ordered state that results in the formation of a crystal. If there are impurities in the liquid, i.e. solutes, the liquid is inherently less ordered. Therefore, a solution is more difficult to freeze than the pure solvent so a lower temperature is required to freeze the liquid.

Osmotic Pressure

Osmosis refers to the flow of solvent molecules past a semipermeable membrane that stops the flow of solute molecules only. When a solution and the pure solvent used in making that solution are placed on either side of a semipermeable membrane, it is found that more solvent molecules flow out of the pure solvent side of the membrane than solvent flows into the pure solvent from the solution side of the membrane. That flow of solvent from the pure solvent side makes the volume of the solution rise. When the height difference between the two sides becomes large enough, the net flow through the membrane ceases due to the extra pressure exerted by the excess height of the solution chamber. Converting that height of solvent into units of pressure (by using the ) gives a measure of the osmotic pressure exerted on the solution by the pure solvent. P stands for pressure, r is the density of the solution, and h is the height of the solution.

shows a typical setup for measuring the osmotic pressure of a solution.

Figure %: Setup for Measuring the Osmotic Pressure of a Solution

You can understand why more molecules flow from the solvent chamber to the solution chamber in analogy to our discussion of Raoult's law. More solvent molecules are at the membrane interface on the solvent side of the membrane than on the solution side. Therefore, it is more likely that a solvent molecule will pass from the solvent side to the solution side than vice versa. That difference in flow rate causes the solution volume to rise. As the solution rises, by the pressure depth equation, it exerts a larger pressure on the membrane's surface. As that pressure rises, it forces more solvent molecules to flow from the solution side to the solvent side. When the flow from both sides of the membrane are equal, the solution height stops rising and remains at a height reflecting the osmotic pressure of the solution.

The equation relating the osmotic pressure of a solution to its concentration has a form quite similar to the ideal gas law:

Although the above equation may be more simple to remember, the 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.