Colligative Properties

When you add a solute to a solvent, both the freezing point and boiling point of the solvent (now a solution) change. Water, of course, is the liquid we will be dealing with most often. The normal freezing point (that is, the freezing point at 1 atm pressure) of pure water is 0C. The normal boiling point of water is 100C. But if you make a solution using water as the solvent, the freezing point of that solution will not be 0C, nor will the boiling point be 100C. (In addition, the vapor pressure of the liquid is reduced; indeed, this is the root of the changes in freezing and boiling points.) The freezing point depression and boiling point elevation (as well as vapor pressure lowering) are all related to one another, and the magnitude of the changes depends on the concentration of solute particles. It is also dependent opon the nature (that is, the identity) of the solvent. These properties are not so much dependent on the nature of, or the chemical properties of, the solute that is dissolved, but simply on the number of solute particles present. It is the concentration of solute particles that make the difference in the vapor pressure and freezing and boiling points. (Of course, that concentration does have to take into account whether that solute dissociates into ions or not). Because of this these properties (freezing point depression, boiling point elevation, and vapor pressure lowering) are all grouped together as a set of properties that are dependent upon the same variables, and they are collectively called colligative properties.

Vapor Pressure Lowering Imagine a solution with no solute in it. The vapor pressure is just the natural vapor pressure of the (pure) solvent, of course, and that vapor pressure depends on the intermolecular forces. If there are strong intermolecular forces between solvent particles, then the vapor pressure is low (because it is difficult for the particles to break off from one another to go into the gaseous state); if the intermolecular forces are weak, then the vapor pressure is higher. This is the natural variation if vapor pressures of different solvents. Now imagine a solvent with solute particles dissolved in it, that is, turned into a solution. Those solute particles get in the way of the evaporation process the solute particles themselves dont evaporate, and they can block

solvent particles from evaporating simply by getting in the way. In this manner, the vapor pressure of a solution is lower than the vapor pressure of the pure solvent; the higher the concentration of solute particles, the more the escape routes of the solvent are blocked, and the lower the vapor pressure of the solution. This is referred to as Raoults Law. Boiling Point Elevation
A solution requires a higher temperature to boil compared to the pure solvent. This is the colligative property called boiling point elevation; that is, the boiling point of a liquid is increased if a solute is dissolved in it. When does boiling occur? A solution boils when the vapor pressure of the solution reaches the external vapor pressure. As you heat up a beaker of water at normal atmospheric pressure, the vapor pressure of the water increases; when it reaches 1 atm, the water boils. If you add a solute and that lowers the vapor pressure, the solution has to be heated to an even higher temperature, to counteract the vapor pressure lowering effect of the solute, to make the solvent boil. Thus the boiling point of a solution is at a higher temperature than the boiling point of a pure solvent.

The antifreeze in a car radiator is an example of this. In the advertisements it's called a summer protection against boil-overs. Essentially what they have done is raised the boiling point of the liquid, of the water, by making it a solution.

In general, for dilute solutions, the amount of change in the boiling point is proportional to the concentration of the solute in the solution. The more solute dissolved, the greater the effect. An equation has been developed for this behavior. It is: Tb = Kb x m

That is, the temperature increase in the boiling temperature of the pure solvent compared to the solution Tb = Tb, solution - Tb, solvent is equal to a constant (Kb) multiplied by the molality (m) of the solution. The freezing point depression equation takes a similar form. Here are some "molal boiling point elevation constants" Kb (the units on the constant are degrees Celsius per molal (C/m) and they are particular for the solvent): Substance (solvent) benzene camphor Ethyl ether Water Kb 2.53 5.95 2.02 0.52

carbon tetrachloride 5.03

Freezing Point Depression

A solution will freeze at a lower temperature than the pure solvent. This is the colligative property called freezing point depression. Freezing point depression results from the change that occurs in the temperature at which a liquid freezes (or a solid melts) when a solute is dissolved in it. Freezing requires the molecules to slow down enough to allow a long-range three-dimensional order; the presence of the solute particles interferes with this long-range order. Thus, a lower freezing point is required, that is, the effect on the freezing point is just the opposite of that on the boiling point. For example, consider the effect that salt has on the melting point of ice (which is the same as the freezing point of water). In the northeast, the salting of roads is very common during the winter; it melts the ice and snow that's present on the roads. Another example of this is the use of antifreeze in car radiators (the name antifreeze makes more sense in the wintertime than in the summertime). By using a solution instead of pure water in the radiator, the liquid will not freeze until you get to some temperature below 0C (which is 32F), rather than freezing right at 0C.

The next time you see a container of antifreeze, look on the label and it will show you that as you increase the amount (concentration, actually) of the antifreeze in the car's cooling system the freezing point of the solution decreases. There is a limit to that, and the instructions usually say that you should not exceed a certain percentage. If you get to the point where you have water in the antifreeze rather than antifreeze in the water, the freezing point starts going back up-although it is still very low. Again, we see that the more solute dissolved, the greater the effect. An equation has been developed for this behavior. It is: Tf = Kf x m. where Tf = Tf, solution Tf, solvent The temperature change from the pure solvent to the solution is equal to a constant that is dependent only on the solvent multiplied by the molality of the solution. Here are some "molal freezing point depression constants" Kf (the units on the constant are degrees Celsius per molal (C/m)): Substance benzene camphor ethyl ether water Kf 5.12 40. 1.79 1.86

carbon tetrachloride 30.

One way of summarizing both freezing point depression and boiling point elevation is to say that the addition of solute extends the temperature range over which the liquid can exist. It will boil at a higher temperature and it will freeze at a lower temperature. Note that as the concentration of the solute increases, so does the effect on both the freezing point and the boiling point. In general, the extent of the boiling or freezing point change is proportional to the number of moles of solute added to a certain amount of water, regardless of what specific chemical is used.

Electrolyte Effect In addition, you have to take into account the degree of dissociation of the solute, because it depends on the number of solute particles interfering with the vaporization or boiling processes. If a strong electrolyte dissociates into two ions, it will be twice as effective at changing the boiling or freezing point. If a strong electrolyte dissociates into three ions, then it is three times as effective as the same number of moles of a nonelectrolyte. If a weak electrolyte dissociates 5%, then it would be 5% more effective than an equal number of moles of a nonelectrolyte. Quantitatively, the vant Hoff factor i allows for a calculation of the boiling point elevation and freezing point depression for electrolytes.

The van't Hoff Factor The van't Hoff factor is symbolized by the lower-case letter i. It is a unitless constant directly associated with the degree of dissociation of the solute in the solvent. For electrolytes we use the equations:

Tf = i Kf m

and

Tb = i Kb m

Non-electrolyte substances, which do not ionizein solution, like sugar, have i = 1. Electrolyte substances which ionize into two ions, like NaCl, have i = 2. Substances which ionize into three ions, like MgCl2, have i = 3.

In the 1880's, when van't Hoff was compiling and examining boiling point and freezing point data, he did not understand what i meant. His use of i was strictly to try and make the data fit together. Essentially, this is what he had: Take a 1.0molal solution of sugar and measure its bp elevation. Now examine a 1.0-molal solution of NaCl. Its bp elevation is twice the sugar's value. When he did MgCl2, he got a value three times that of sugar. All his values began to group together, one groups with sugar-like values, another with NaCl-like values and a third with MgCl2like values. This is how each type of compound got its i value.