Chapter 7: Colligative Properties

In colder countries where temperature may reach to 00 c an

antifreeze, ethylene glycol, is used to prevent water in
automobiles from freezing. The antifreeze does this by lowering
the freezing point of water.
This I only one of several properties of solutions that will be
discussed in this chapter. As you go through this chapter you
will learn more about the effects of the presence of solutes on
the physical properties of solvents.

At the end of this chapter, you should be able to answer the

following question:
1. What is the relationship between the vapor pressure of a
solution and the concentration of solute?
2. How does concentration affect the boiling point and the
freezing point of a solution?
3. How can osmotic pressure be used to calculate molecule mass?
4. How do the colligative properties of nonelectrolyte
solutions differ from those of electrolyte solutions?

Section 1

Vapor Pressure Lowering

Colligative properties are properties that depend only on the
concentration of the solute and not on the nature of the solute.
In our study about liquids, we defined a quantity called vapor
pressure. Remember that vapor pressure is the pressure exerted by
the vapor above the liquid. Solutions also exert vapor pressure.
The rate at which liquids vaporize is determined by the kinetic
energy of the molecules which escape from the liquid phase to the
vapor phase. Hence, in accordance with the kinetic molecular
theory, vapor pressure increases as temperature increases. The
tendency of the molecules to escape from the liquid phase to the
vapor pressure is dependent also on the strength of
intermolecular forces of attraction. In the presence of a
nonvolatile solute, the tendency of the molecules on the surface
of a liquid to escape into the vapor phase is decreased due to
the solute-solvent attraction. This causes the vapor pressure of
the liquid to decrease. We will therefore observe a solution
containing a nonvolatile solute such as salt and sugar to have
lower vapor pressure than the pure solvent.
This relationship was observed by Francois Marie Raoult in
1887. It is expressed by Raoult’s law which states that at
constant temperature, the vapor pressure of the solvent over a
solution, P, is the product of the vapor pressure of the pure
solvent ( Po ) and the mole fraction of the solvent in the
solution ( X 1 ).

P= X 1 P o

In a solution containing only one solute, X 1 =1- X 2 where X 2

is the mole fraction of the solute. The equation above can them
be rewritten as:

P=(1- X 2 ) P01 or

P= P01 - X 2 P 01
Therefore,
0 0
P1 -P=∆P= X 2 P 1
Note that ∆P is the decrease in vapor pressure and is directly
proportional to the solute concentration in mole fraction.
Let us look at the following example.
Sample problem:
Calculate the vapor pressure of a solution made by dissolving
82.4g of urea (molar mass 60.06g/mol) in 212mL of water at 35o
C. what is the vapor pressure lowering? The vapor pressure of
water at 35o C is 42.18mm Hg.
Solution:
82.4 g
nurea =
60.06 g /mol
= 1.37mol
g 1mol
nwater =(212mL ÷ 1 )(
mL 18.02 g
= 11.8ml
 1.37 mol
∆P=( )(42.18mm Hg)
1.37 mol +11.8 ml
= 4.39MM Hg
Section 2
Boiling Point Elevation and Freezing Point Depression
Activity: which boils highest?
Objective: to determine which among the three samples will boil
at the highest temperature: pure distilled water, diluted salt
water solution, or concentrated salt water solution.
Materials: 3 breakers, salt, distilled water, hot plate or Bunsen
burner, and thermometers
Before doing the activity, predict which among the three liquids
will have the highest boiling point: pure distilled water,
diluted salt water solution, or concentrated salt water solution.

Procedure:
1. Pour equal amounts of distilled water in three separate
beakers.
2. In the first beaker, dissolve salt until the solution is
saturated. Note the amount of salt used.
3. In the second beaker, dissolve half the amount of salt used
in the first beaker to form an unsaturated solution.
4. In the last beaker, leave pure distilled water.
5. Heat the three liquids.
6. Record the temperature of the liquids at their respective
boiling points.
Boiling means heating a liquid such that the vapor pressure of
the liquid equals that of the external pressure which, under
normal conditions, is the atmospheric pressure. The temperature
at which the vapor pressure of a liquid equals the atmospheric
pressure is called the boiling point.
The previous section discussed how the presence of nonvolatile
solutes can lower the vapor pressure of a solution. Since the
boiling point of a solution is related to vapor pressure, the
boiling point is also affected by the presence of solutes. The
lower vapor pressure of the solution means that at the boiling
point of the pure solvent, the solution will not yet boil since
at this temperature its vapor pressure is lower than the
atmospheric pressure. Thus, the solution must be heated for the
vapor pressure to increase and be equal to the atmospheric
pressure. This makes the boiling point of the solution higher
than the boiling point of the pure solvent. The difference in the
boiling point of the solution from the solvent is called boiling
point elevation.
The boiling point elevation, ∆ T b , is proportional to the
concentration of the solution. In mathematical terms,
∆ T b = Kb m
Where k, is the molal boiling point elevation constant, and m is
the molal concentration of the solution. The molal boiling point
elevation constant is an intensive property and is a
characteristic only of one particular solvent (table 7.1). The
boiling point of the solution can be computed by adding the
computed ∆ T b to the boiling point of the pure solvent.

T b solution = T b solvent +∆ T b

T b solution = T b solvent + K b m

Table 7.1 Molal boiling point elevation constant and molal

freezing point depression constant of common liquids
Solvent Normal Freezing K, Normal Boiling Kb
Point( C o ) ( Point( C o ¿ ( C o /m¿
o
C /m¿

Water 0 1.86 100.0 0.52

Benzene 5.5 5.12 80.1 2.53
Ethanol 117.3 1.99 78.4 1.22
Acetic acid 16.6 3.90 117.9 2.93
cyclohexane 6.6 20.00 80.7 2.79

For example, a 2.0 molal solution of water and urea, a

nonvolatile, nonelectrolyte will boil at 101.0 4 o C rather than
at 100. 0o C . to arrive at this answer, you will need to
multiply the molal concentration of the solution with the molal
boiling point elevation constant of water,
∆ T b = Kb m
oC
∆ T b =(0.52 )(2.0M)=1.0 4o C
M
Adding ∆ T b to the normal boiling point of water, the boiling
point of the solution is computed:
T b solution =100. 0o C +∆ T b = 101. 0 4 o C

Based on the equation above, the boiling point temperature of the

solution is higher than that of the pure. Hence, the colligative
properties is called boiling point elevation. Is this consistent
with what you have observed in the activity?
Activity: Stringing Ice
This is a simple yet fun activity that demonstrates the effect of
the presence of a solute on the freezing point. You will need in
this activity a string of yarn, salt, and small cubes of ice.