Colligative properties of solutions are properties that depend on

the concentration of solute molecules or ions in solution but not

on the chemical identity of the solute (whether it is ethylene glycol
or urea, for instance).

There are four colligative properties to consider:

▪ Vapor pressure lowering (Raoult’s Law)
▪ Freezing point depression
▪ Boiling point elevation
▪ Osmotic pressure
▪ A solvent in a closed container reaches a state of
dynamic equilibrium.

▪ The pressure exerted by the vapor in the

headspace is referred to as the vapor pressure of
the solvent.

▪ The addition of any nonvolatile solute (one with

no measurable vapor pressure) to any solvent
reduces the vapor pressure of the solvent.
▪ Nonvolatile solutes reduce the ability of the surface solvent
molecules to escape the liquid.
▪ Vapor pressure is lowered.

▪ The extent of vapor pressure lowering depends on the amount of

solute.
▪ Raoult’s Law quantifies the amount of vapor pressure lowering
observed.
Raoult’s Law: Raoult's law states that a solvent's partial
vapour pressure in a solution (or mixture) is equal or
identical to the vapour pressure of the pure solvent
multiplied by its mole fraction in the solution.
PA = XAPAo
where PA = partial pressure of the solvent vapor above the
solution (i.e. with the solute)

XA = mole fraction of the solvent

PoA = vapor pressure of the pure solvent.

Example: The vapor pressure of water at 20oC is 17.5 torr.
Calculate the vapor pressure of an aqueous solution prepared
by adding 36.0 g of glucose (C6H12O6) to 14.4 g of water.

Given: PoH2O= 17.5 torr

mass solute = 36.0 g of glucose mass
solvent = 14.4 g of water

Find: PH2O

Raoult’s Law: PA = XAPAO

Solution:

Answer: 14.0 torr

Example: The vapor pressure of pure water at 110 oC is 1070 torr. A
solution of ethylene glycol and water has a vapor pressure of
1.10 atm at the same temperature. What is the mole fraction of
ethylene glycol in the solution?
Given:
▪ PoH2O = 1070 torr
▪ Psolution = 1.10 atm

Find: XEG

Solution:
Answer: XEG = 0.219
Ideal solutions are those that obey Raoult’s Law.

Real solutions show approximately ideal behavior when:

▪ The solution concentration is low.
▪ The solute and solvent have similarly sized molecules.
▪ The solute and solvent have similar types of intermolecular
forces.
Raoult’s Law breaks down when solvent-solvent and solute-
solute intermolecular forces of attraction are much stronger or
weaker than solute-solvent intermolecular forces.
▪ Vapor pressure above solution is vapor pressure of solvent times
mole fraction of solvent in solution

▪ Vapour pressure lowering follows:

▪ The addition of a nonvolatile solute causes solutions to have
higher boiling points than the pure solvent.
▪ Vapor pressure decreases with addition of non-volatile solute.
▪ Higher temperature is needed in order for vapor pressure to
equal 1 atm.
▪ Vapour pressure is always lower
▪ Boiling point is always higher
▪ Freezing point is always lower
▪ Osmotic pressure drives solvent from lower concentration
to higher concentration
◼ The change in boiling point is proportional to the number of
solute particles present and can be related to the molality of
the solution:

∆Tb = Kb.m

where ∆Tb = boiling point elevation

Kb = molal boiling point elevation constant
m = molality of solution

The value of Kb depends only on the identity of the solvent.

 Tb = kb m
The boiling point of a solution containing 40.0 g of an
unknown substance dissolved in 100.0 g of water is 105.3
oC .

Calculate the molar mass of the compound.

▪ Since the solvent is water, the change in temperature (∆T)

would be 105.3 - 100.0 oC = 5.3 oC. You can also find the
Kb in the table in your textbook, kb = 0.512 oC kg/mol.

▪ From this data, you can calculate the molality:

m = ∆Tb / Kb = 5.3 oC / 0.512 oC kg/mol = 10.4 mol/kg
▪ Molality is also defined as the moles of solute per kg of solvent:
m = n /(kg solvent), can be rearranged to be
n = m (kg of solvent)
n = 10.4 mol /kg (0.1000 kg) = 1.04 mol of solute.
▪ The molar mass can be calculated by using the equation.
MW = m/n MW = 40.0 g / 1.04 mol = 38.5 g/mol
A solution containing 4.5 g of glycerol, a nonvolatile
nonelectrolyte, in 100.0 g of ethanol has a boiling point of 79.0
oC. If the normal BP of ethanol is 78.4 oC, calculate the molar

mass of glycerol.
Example:

A solution containing 4.5 g of glycerol, a nonvolatile nonelectrolyte, in 100.0 g

of ethanol has a boiling point of 79.0 oC. If the normal BP of ethanol is 78.4oC,
calculate the molar mass of glycerol.

Given:
∆Tb = 79.0 oC - 78.4 oC = 0.6 oC
mass solute = 4.5 g
mass solvent = 100.0 g = 0.100 kg
Kb = 1.22oC/m

Find: molar mass (g/mol)

Step 1: Calculate molality of solution

Step 2: Calculate moles of solute present

Step 3: Calculate molar mass

▪ The addition of a nonvolatile solute causes solutions to have
lower freezing points than the pure solvent.
▪ Freezing point of the solution is lower than that of the pure
solvent.
▪ Not all ionic substances dissociate completely, hence Van’t Hoff
factor accounts for this.

▪ Van’ t Hoff factor:

i = moles of particles in solution/moles of solute dissolved
Analogous to boiling point, the freezing point depression is
proportional to the molal concentration of solute particles

T f = K f m
For solutes which are not completely dissociated, the van’t
Hoff factor is applied to modify m:
▪ The magnitude of the freezing point depression is proportional
to the number of solute particles and can be related to the
molality of the solution.
▪ ∆Tf = Kf . m
Where:
∆Tf = freezing point depression
Kb = molal freezing point depression constant
m = molality of solution

▪ The value of Kf depends only on the identity of the solvent.

Example: Calculate the freezing point depression of a solution
that contains 5.15 g of benzene (C6H6) dissolved in 50.0 g of CCl4.
Given:
mass solute =
mass solvent =
Kf solvent =

Find: ∆Tf
 Exercise
▪ Estimate the freezing point of a 2.00 L sample of seawater (kf = 1.86 oC kg /
mol), which has the following composition:
0.458 mol of Na+ 0.052 mol of Mg2+ 0.010 mol Ca2+
0.533 mol Cl- 0.002 mol HCO3- 0.010 mol K+ 0.001 mol Br-
0.001 mol neutral species
Since colligative properties are dependent on the NUMBER of particles and not
the character of the particles, you must first add up all the moles of solute in
the solution.
Total moles = 1.067 moles of solute. Now calculate the molality of the solution:
m = moles of solute / kg of solvent = 1.067 mol / 2.00 kg
m = 0.5335 mol/kg
Last calculate the temperature change:
∆Tf = - kf m = -(1.86 oC kg/mol) (0.5335 mol/kg) = 0.992 oC The freezing point
of seawater is T solvent - ∆T = 0 oC - 0.992 oC
∆Tf = - 0.992 oC
Some substances form semipermeable membranes, allowing some
smaller particles to pass through, but blocking other larger
particles.

In biological systems, most semipermeable membranes allow

water to pass through, but solutes are not free to do so.

If two solutions with identical concentration (isotonic solutions)

are separated by a semipermeable membrane, no net movement
of solvent occurs.
▪ Osmosis: the net movement of a solvent through a
semipermeable membrane toward the solution with
greater solute concentration.
▪ In osmosis, there is net movement of solvent from the
area of lower solute concentration to the area of
higher solute concentration.
▪ Movement of solvent from high solvent concentration
to low solvent concentration.
Osmosis plays an important role in living
systems:
▪ Membranes of red blood cells are
semipermeable.
▪ Placing a red blood cell in a hypertonic
solution (solute concentration outside the
cell is greater than inside the cell) causes
water to flow out of the cell in a process
called crenation.
▪ Placing a red blood cell in a hypotonic
solution (solute concentration outside
the cell is less than that inside the cell)
causes water to flow into the cell.
▪ The cell ruptures in a process called
hemolysis.
Other everyday examples of osmosis:
▪ A cucumber placed in brine solution loses water and becomes a
pickle.
▪ A limp carrot placed in water becomes firm because water
enters by osmosis.
▪ Eating large quantities of salty food causes retention of
▪ water and swelling of tissues (edema).
▪ Osmotic pressure is a colligative property of a
solution
▪ ᴨ= MRT

▪ ᴨ related to molar concentration of the solute

▪ M =Molarity
▪ R = Gas Constant
▪ T = Temperature
There you found that a solution that is about 0.02 m has a freezing-point
depression of about 0.04 oC. The molarity and molality of a dilute aqueous
solution are approximately equal (see Example 12.7). Therefore, this solution
will also be about 0.02 M. Hence, the osmotic pressure at 25 oC (298 K) is?
= MRT
= 0.02 mol/L x 0.082 Latm/(Kmol) x 298 K
= 0.5 atm