Physical Properties of Solutions

The physical properties of a solution are different from those of the pure solvent. Many
differences in physical properties are predictable if the solute in the pure state is
nonvolatile - that is, if it has a very low vapor pressure. Sugar, sodium chloride, and
potassium nitrate are examples of nonvolatile solutes. The word “colligative” comes from
two Latin words meaning “to tie together”. Colligative properties are those physical
properties of solutions of nonvolatile solutes that depend only on the number of particles
(molecules or ions) present in a given amount of solution, not on the nature of those
particles. We will consider four colligative properties: vapor pressure lowering, boiling
point elevation, freezing point depression, and osmotic pressure.

Vapor Pressure Lowering

The vapor pressure of a liquid is determined by how easily its molecules are able to
escape the surface of the liquid and enter the gaseous phase. When a liquid evaporates
easily, it will have a relatively large number of its molecules in the gas phase and thus
will have a high vapor pressure.

Figure below shows the surface of a pure solvent compared to a solution. In the picture

on the left, the surface is entirely occupied by liquid molecules, some of which will
evaporate and form a vapor pressure. On the right, a nonvolatile solute has been
dissolved into the solvent. Nonvolatile means that the solute itself has little tendency to
evaporate. Because some of the surface is now occupied by solute particles, there is less
room for solvent molecules. This results in less solvent being able to evaporate. The
addition of a nonvolatile solute results in a lowering of the vapor pressure of the solvent.

The solution on the right left has had some of its solvent particles replaced by solute
particles. Since the solute particles do not evaporate, the vapor pressure of the solution
is lower than that of the pure solvent.

The lowering of the vapor pressure depends on the number of solute particles that have
been dissolved. The chemical nature of the solute is not important because the vapor
pressure is merely a physical property of the solvent. The only requirement is that the
solute only dissolved and does not undergo a chemical reaction with the solvent. 
While the chemical nature of the solute is not a factor, it is necessary to take into
account whether the solute is an electrolyte or a non electrolyte (Substances that give
ions when dissolved). Recall that ionic compounds are strong electrolytes and thus
dissociate into ions when they dissolve. This results in a larger number of dissolved
particles. For example, consider two different solutions of equal concentration. One is
made from the ionic compound sodium chloride, while the other is made from the
molecular compound glucose. The following equations show what happens when these
solutes dissolve.

NaCl(�)→Na+(��)+Cl−(��)2 dissolved
particlesC6H12O6(�)→C6H12O6(��)1 dissolved particle

The sodium chloride dissociates into two ions, while the glucose does not dissociate.
Therefore, equal concentrations of each solution will result in twice as many dissolved
particles in the case of the sodium chloride. The vapor pressure of the sodium chloride
solution will be lowered twice the amount as the glucose solution.

In order to figure out how much the solute has affected the vapor pressure, we need to
approximate how many fewer molecules are able to reach the surface of the liquid,
correct? A good approximation of how many molecules there are of solvent versus solute
is the mole fraction, Xsolvent. If we simply multiply the new mole fraction of solvent by the
standard vapor pressure (Posolvent) of the pure solvent, this will give us a good
approximation of the new vapor pressure of the solvent. The equation would look like
Psolvent = Xsolvent Posolvent. This equation is called Raoult's Law (showed by Francois-Marie
Raoult) . Note that the pressure you obtain from this equation is the new equilibrium
vapor pressure of the system with the solute included. If you want to know how much
change has taken place, you will need to look at the difference between the new
Psolvent and the original Posolvent of the pure solvent (in other words subtract one from the
other) DP = Psolvent - Posolvent = change in the vapor pressure of the system. For almost all
non-volatile solvents, this change will be a negative value.

Limitations on Raoult's Law:

Raoult's law only works for low concentration solutions. Why? Well, in order for our
approximation to work, the interactions between the solute and solvent molecules must
be nearly identical. If the interactions are stronger, then the heat of vaporization of the
solvent will change and thus our whole approximation falls apart. Since we know that
intermolecular forces vary greatly between molecules, the affect of those forces must be
kept at a minimum by keeping the solute concentration real low. You can think of it as
having one stinky guy at a party in a room of 1000 people, there is a very good chance
that you won't have to smell him, but if there were 100 stinky guys in the room, it would
ruin the whole party, right?

Another consideration is the type of solute. If the solute is an ionic species (a salt) then it
is most likely going to split up into its component ions when it hits the solvent (normally
water). If this is the case, we need to consider each particle that forms. For instance, if
you added 0.25 moles of NaCl to a solution, you would actually be adding 0.25 moles of
Na+ and 0.25 moles of Cl- for an overall colligative affect of 0.50 moles of ions. This value
of 2 x 0.25 is called the van't Hoff factor (i) and must be used whenever you calculate
colligative properties of solutions containing ion