Colligative Properties of

Solutions

Introduction and Summary

Solutions, especially liquid solutions, generally have markedly

different properties than either the pure solvent or the solute. For
example, a solution of sugar in water is neither crystalline like
sugar nor tasteless like water. Some of the properties unique to
solutions depend only on the number of dissolved particles and
not their identity. Such properties are called colligative
properties. The colligative properties we will consider in this
SparkNote are vapor pressure lowering, freezing point
depression, boiling point elevation, and osmotic pressure.

When a nonvolatile solute is dissolved in a solvent, the vapor

pressure of the resulting solution is lower than that of the pure
solvent. The amount of the vapor pressure lowering is
proportional to the amount of solute and not its identity.
Therefore, vapor pressure lowering is a colligative property. The
equation that describes that phenomenon is called Raoult's law.

Boiling point elevation is a colligative property related to vapor

pressure lowering. The boiling point is defined as the
temperature at which the vapor pressure of a liquid equals the
atmospheric pressure. Due to vapor pressure lowering, a
solution will require a higher temperature to reach its boiling
point than the pure solvent.

Every liquid has a freezing point--the temperature at which a

liquid undergoes a phase change from liquid to solid. When
solutes are added to a liquid, forming a solution, the solute
molecules disrupt the formation of crystals of the solvent. That
disruption in the freezing process results in a depression of the
freezing point for the solution relative to the pure solvent.

When a solution is separated from a volume of pure solvent by a

semi-permeable membrane that allows only the passage of
solvent molecules, the height of the solution begins to rise. The
value of the height difference between the two compartments
reflects a property called the osmotic pressure of a solution. As
you know, if you add more solvent to a solution, the two mix
together to form a more dilute solution. The same forces allowing
that mixing serve to force solvent molecules from the pure
solvent compartment across the membrane into the solution
compartment causing the change in volume. The amount of
osmotic pressure is directly related to the concentration of the
solute. That is because more concentrated the solutions have
greater potentials for dilution.

Colligative Properties of
Solutions

Terms

Colligative Property - A property that depends only on the

amount of solute in a solution and not the identity of the solute.

Concentrated - A solution of high concentration.

Concentration - The amount of solute dissolved in a given

amount of solvent.

Dilute - A solution of low concentration or the process of

lowering the concentration of a solution by the addition of
solvent.

Dilution - The decrease of the concentration of a solution by

the addition of more solvent.

Dissolve - To become a part of a solution.

Nonvolatile - A substance that does not have an appreciable
vapor pressure.

Raoult's Law - The vapor pressure of a solution is the product

of the mole fraction of the solvent and the vapor pressure of the
pure solvent.

Solubility - The amount of a particular solute that can dissolve

in a given amount of a particular solvent. Solubilities are
generally listed in g / L.

Solute - A minor component of a solution.

Solution - A homogeneous mixture.

Solvent - The major component of a solution.

Colligative Properties of
Solutions

Colligative Properties

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.

Figure 1.1: The Vapor Pressure of a Solution is Lower than that of

the Pure Solvent
The French chemist Francois Raoult discovered the law that
mathematically describes the vapor pressure lowering
phenomenon. Raoult's law is given in :

Figure 1.2: Raoult's Law Describes the Mathematics of Vapor

Pressure Lowering
Raoult's law states that the vapor pressure of a solution, P,
equals the mole fraction of the solvent, csolvent, multiplied by the
vapor pressure of the pure solvent, Po. While that "law" is
approximately obeyed by most solutions, some show deviations
from the expected behavior. Deviations from Raoult's law can
either be positive or negative. A positive deviation means that
there is a higher than expected vapor pressure above the
solution. A negative deviation, conversely, means that we find a
lower than expected vapor pressure for the solution. The reason
for the deviation stems from a flaw in our consideration of the
vapor pressure lowering event--we assumed that the solute did
not interact with the solvent at all. That, of course, is not true
most of the time. If the solute is strongly held by the solvent, then
the solution will show a negative deviation from Raoult's law
because the solvent will find it more difficult to escape from
solution. If the solute and solvent are not as tightly bound to each
other as they are to themselves, then the solution will show a
positive deviation from Raoult's law because the solvent
molecules will find it easier to escape from solution into the gas
phase.
Solutions that obey Raoult's law are called ideal solutions
because they behave exactly as we would predict. Solutions that
show a deviation from Raoult's law are called non-ideal solutions
because they deviate from the expected behavior. Very few
solutions actually approach ideality, but Raoult's law for the ideal
solution is a good enough approximation for the non- ideal
solutions that we will continue to use Raoult's law. Raoult's law is
the starting point for most of our discussions about the rest of the
colligative properties, as we shall see in the following section.

Boiling Point Elevation

One consequence of Raoult's law is that the boiling point of a

solution made of a liquid solvent with a nonvolatile solute is
greater than the boiling point of the pure solvent. The boiling
point of a liquid or is defined as the temperature at which the
vapor pressure of that liquid equals the atmospheric pressure.
For a solution, the vapor pressure of the solvent is lower at any
given temperature. Therefore, a higher temperature is required
to boil the solution than the pure solvent. is a phase diagram for
both a pure solvent and a solution of that solvent and a
nonvolatile solute that explains that point graphically.
 Figure 1.3: Phase Diagram for a Solvent and its Solution with a
Nonvolatile Solute
As you can see in the the vapor pressure of the solution is lower
than that of the pure solvent. Because both pure solvent and
solution need to reach the same pressure to boil, the solution
requires a higher temperature to boil. If we represent the
difference in boiling point between the pure solvent and a
solution as DTb, we can calculate that change in boiling point
from the :

In the we use the units molality, m, for the concentration, m,

because molality is temperature independent. The term Kb is a
boiling point elevation constant that depends on the particular
solvent being used. The term i in the above equation is called the
van't Hoff factor and represents the number of dissociated moles
of particles per mole of solute. The van't Hoff factor is 1 for all
non-electrolyte solutes and equals the total number of ions
released for electrolytes. Therefore, the value of i for Na2SO4 is 3
because that salt releases three moles of ions per mole of the
salt.

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 1.5: 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 1.8: 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.

Colligative Properties of
Solutions

Problems and Solutions

Problem 1.1:
What is the vapor pressure of the pure solvent if the vapor
pressure of a solution of 10 g of sucrose (C6H12O6) in 100 g of
ethanol (C2H6O) is 55 mmHg?

Solution for Problem 1.1

To solve this problem, we will use Raoult's law:

Then rearrange the equation to solve for the pressure of the pure
solvent, Po. After converting the gram amounts to moles we find
that the mole fraction of the solvent ethanol is 0.975. Therefore,
the vapor pressure of the solvent is 56.4 mmHg.

Problem 1.2:
What is the freezing point of a solution of 15.0 g of NaCl in 250 g
of water? The molal freezing point constant, Kf, for water is 1.86
o
C kg / mol.

Solution for Problem 1.2

DTf = - i Kf m

For NaCl, i = 2. The concentration of the solution is 1.03 m in

NaCl. Therefore, the change in the freezing point of the water is
-3.8 oC. The freezing point of the solution is, therefore, -3.8 oC.

Problem 1.3:
A solution of 0.5 g of an unknown nonvolatile, nonelectrolyte
solute is added to 100 mL of water and then placed across a
semipermeable membrane from a volume of pure water. When
the system reaches equilibrium, the solution compartment is
elevated 5.6 cm above the solvent compartment. Assuming that
the density of the solution is 1.0 g / mL, calculate the molecular
mass of the unknown.

Solution for Problem 1.3

To solve this problem, we will rearrange the formula for osmotic
pressure:

Then we can calculate the pressure from the pressure depth

equation, then convert the units into atmospheres.

Next, we can calculate the molarity of the solution. Finally, we

will use that molarity to calculate the molar mass of the unknown
from the volume of the solution and the mass of the unknown.