8.

3 Colligative Properties
Objective :
At the end of this lesson students should be able to:
(a)
(b)

Define colligative properties.

Describe the colligative properties of a solution:
i.
ii.
iii.
iv.

(c)

lowering of vapour pressure

boiling point elevation
freezing point depression
osmotic pressure

Perform calculations on colligative properties of

a non-electrolyte solution containing non-volatile
solutes.

KEYWORDS
colligative properties
boiling point elevation

freezing point depression

vapor pressure lowering

osmotic pressure

COLLIGATIVE PROPERTIES
Properties depend only on the number of
solute particles in the solution and not
their chemical identity
Colligative means
collective

There are 4 colligative properties;

COLLIGATIVE PROPERTIES OF NONVOLATlLE

NONELECTROLYTES SOLUTIONS
Vapor Pressure Lowering
o

Psolution = Xsolvent x Psolvent

or

P = XsoluteP solvent

Boiling Point Elevation

Tb = Kb m
Freezing point Depression
Tf = Kf m
Osmotic Pressure

= MRT

NONVOLATILE SOLUTES
Have negligible vapor pressure
Do not dissociates into ions
EXAMPLE:
Sucrose (table sugar)
Ethylene glycol
Glycerol
Proteins
Urea

VAPOR PRESSURE LOWERING (P)

Vapor pressure of a solution of a nonvolatile
is always lower than the vapor pressure of
pure solvent

Pure solvent

Solution = Solvent + Solute

Present of solute molecules hinder the escape of

solvent molecules at or near the surface into vapor
Number of solvent molecules in the vapor reduced
Vapor pressure of the solution lower than that of
pure solvent

According to Raoults Law, the vapor pressure

of a solution containing a nonvolatile solute
is equal to the vapor pressure of pure solvent
times the mole fraction of solvent
o

Psolution = Xsolvent x Psolvent

Another method of calculation:

According to Raoults Law :
o

Psolvent = Xsolvent x Psolvent

Xsolvent + Xsolute = 1

Xsolvent = 1 Xsolute

Thus,

Psolvent = Xsolvent x Psolvent

Psolvent = (1 Xsolute) x Psolvent

Psolvent = Psolvent (Xsolute x Psolvent)

Psolvent Psolvent = (Xsolute x Psolvent)

P = Xsolute x Psolvent

o
o
o

EXAMPLE
Carbon tetrachloride (CCl4) has a vapor pressure
of 100 torr at 23oC. This solvent can dissolves
candle wax, which is essentially nonvolatile.
Molecular formula of candle wax = C22H46
What is the vapor pressure at 23oC of a solution
prepared by dissolving 10.0 g of wax in
40.0 g of CCl4?

Ans: EXAMPLE
Mole of wax =
(solute) (C22H46)

10.0 g
310 g/mol

= 0.0323 mol wax

40.0 g

Mole of CCl4 =
= 0.260 mol CCl4
154 g/mol
(solvent)
X

CCl4=

Mol of CCl4
Total mol (wax + CCl4)
0.260 mol

(0.0323 + 0.260) mol

= 0.889

Ans: EXAMPLE
X

0.889
=
CCl

Solvent = CCl4

According to Raoults Law:

Psolution = Xsolvent x Psolvent o
Psolution

=X

x P
CCl4

o
CCl4

= 0.889 x 100 torr

=

88.9 torr

BOILING POINT ELEVATION (Tb)

o

Psolution < Psolvent

Tb (boiling point) is the temperature when
Psolution = Patmosphere
Higher temperature needed to raise the
vapor pressure of the solution (Psolution)
to equal the external pressure (Patmosphere)
A solution boils at
higher temperature than
the pure solvent

TOPIC 8 : PHASE EQUIBLIBRIA

Tb is proportional to the concentration of

of solute particles:
Tb m
Tb = Kbm
= Tb(solution) Tb(pure solvent)
Kb: molal boiling point elevation constant
Unit: oC/m oC Kg mol1
***Kb solution is given
m: the solution molality
Unit: molal

Tb > 0

EXAMPLE
0.01 moles of sucrose dissolved in 100 g water.
What is the boiling point of the aqueous solution
at 1 atm? Kb for water is 0.512 oC/m.

Ans: EXAMPLE
Nonvolatile solute = sucrose
Molality of
=
sucrose solution
=

Solvent = water

Mol of sucrose
Kg of water
0.01 mol
= 0.1 m
0.1 Kg

Tb = Kbm
= 0.512 oC/m x 0.1 m

= 0.051 oC

Tb(solution) = Tb(pure water) + Tb

= (100 + 0.051) oC

= 100.051 oC

FREEZING POINT DEPRESSION (Tf)

The addition of solute reduce number of
solvent molecules that can enter the solid
phase
The dynamic equilibrium disrupted and can
be reestablished only at lower temperature

TOPIC 8 : PHASE EQUIBLIBRIA

Tf is proportional to the concentration of

of solute particles:
Tf m
Tf = Kfm
= Tf(pure solvent) Tf(solution)

Tf > 0

Kf: molal freezing point depression constant

Unit: oC/m oC Kg mol1
***Kf solution is given
m: the solution molality
Unit: molal

EXAMPLE
What is the freezing point of a solution
containing 478 g of ethylene glycol
(antifreeze) in 3202 g of water? The molar
mass of ethylene glycol is 62.01 g.
Kf of water = 1.86oC/m

Ans: EXAMPLE
Solute: ethylene glycol
Mol of ethylene glycol =
=

Solvent: water
Mass
Molar mass
478 g
62.01 g/mol

= 7.708 mol ethylene glycol

Molality of solution =
=

Mol of ethylene glycol

Kg of water
7.708 mol
= 2.407 m
3.202 Kg

Ans: EXAMPLE
Tf = Kfm
= 1.86 oC/m x 2.407 m
= 4.48 oC

Tf(solution) = Tf(pure water) Tf

= (0.00 4.48) oC
= 4.48 oC

OSMOSIS
Applies only to aqueous solution
Two solutions of different concentrations are
separated by a semipermeable membrane
The membrane allows water (solvent), but
not solute, to pass through

The net flow of water:

from dilute to more concentrated solution
increases the volume of the solution
decreases its concentration

dilute

more
concentrated

TOPIC 8 : PHASE EQUIBLIBRIA

OSMOTIC PRESSURE ()
The applied pressure required to stop osmosis
Prevent volumes changes

mol of solute
volume of solution

M (molarity of solution)
= MRT

R: gas constant
T: absolute temperature (in K)

EXAMPLE
A very diluted solution, 0.0010 M sugar in water,
is separated from pure water by an osmotic
membrane.
What osmotic pressure in torr develop 25oC?

Ans: EXAMPLE
Solute: sugar

Solvent: water

T = (273 + 25) K
= 298 K
= MRT

= 0.0010 molL1 x 0.08206 L atm mol1K1 x 298 K

= 0.0245 atm x
= 18.6 torr

760 torr
1 atm

The effect of a nonvolatile solute on

the phase diagram for water.
When a non volatile solute is added to pure solvent, the
mole fraction decreases. Addition of a solute at constant T
and P lowers the solvent chemical potential.