COLLIGATIVE

PROPERTIES

Vapour pressure
Boiling point
Freezing point
Osmotic pressure
 LEARNING
OBJECTIVES
 Describe meaning of colligative property
 Use Raoult’s law to determine vapor pressure of
solutions
 Describe physical basis for vapor pressure
lowering
 Predict magnitude of vapor pressure lowering
based on chemical formula
 Calculate osmotic pressure in solution and use to
determine molar mass of solute
 Predict direction of deviation in non-ideal cases
based on intermolecular forces
 PHYSICAL VS
CHEMICAL
 Mixing is physical process; chemical
properties don’t change
 Properties of solutions are similar to those
of the pure substances
 Addition of a foreign substance to water
alters the properties slightly
 COLLIGATIVE: PARTICLES ARE
PARTICLES
 Colligative comes from colligate – to tie together
 Colligative properties have common origin
 Colligative properties depend on amount of
solute but do not depend on its chemical identity
 Solute particles exert their effect merely by
being rather than doing
 The effect is the same for all solutes
 NON-VOLATILE SOLUTES AND
RAOULT’S LAW
 Vapor pressure of solvent in solution containing non-
volatile solute is always lower than vapor pressure
of pure solvent at same T
 At equilibrium rate of vaporization = rate of condensation
 Solute particles occupy volume reducing rate of evaporationthe
number of solvent molecules at the surface
 The rate of evaporation decreases and so the vapor pressure
above the solution must decrease to recover the equilibrium
 MOLECULAR VIEW OF
RAOULT’S LAW:
BOILING POINT
 ELEVATION
In solution vapor
pressure is reduced
compared to pure
solvent
 Liquid boils when
vapor pressure =
atmospheric pressure
 Must increase T to
make vapor pressure
= atmospheric
 MOLECULAR VIEW OF
RAOULT’S LAW:
FREEZING POINT
DEPRESSION

 Depends on the solute only being in the liquid

phase
 Fewer water molecules at surface: rate of freezing drops
 Ice turns into liquid
 Lower temperature to regain balance
 Depression of freezing point
 ROULT’S LAW

 Vapor pressure above solution is vapor

pressure of solvent times mole fraction of
solvent in solution

Psoln  Psolv X
 Vapour pressure lowering follows:
solv

Psoln  Psolv X solute

 Like ideal gas law, Raoult’s Law works for an
ideal solution
 Real solutions deviate from the ideal
 Concentration gets larger
 Solute – solvent interactions are unequal
 Solvent – solvent interactions are stronger than
the solute – solvent: Pvap is higher
 Solvent – solute interactions are stronger than
solvent – solvent interactions: Pvap is lower
 INCOMPLETE
DISSOCIATION
 Not all ionic
substances dissociate
completely
 Van’t Hoff factor

accounts for
this
Van’ t Hoff
factor:
i = moles of particles in
soln/moles of solute
 RIDING HIGH ON A DEEP
DEPRESSION
 Blue curves are phase
boundaries for pure solvent
 Red curves are phase
boundaries for solvent in
solution
 Freezing point
depression
 Pure solid separates out at
freezing – negative ΔTf
 Boiling point elevation
 Vapour pressure in solution is
lower, so higher
temperature is required to
reach atmospheric – positive
ΔTb
 MAGNITUDE OF
ELEVATION
 Depends on the number of particles
present
 Concentration is measured in
(independent of T) Tb  K b m
molality
 Kb is the molal boiling point elevation
constant
 Note: molality is calculated in terms of
particles
 MAGNITUDE OF
DEPRESSION
 Analagous to boiling point, the freezing
point depression is proportional to the
molal concentration of solute particles

T f  K f
m are not completely
 For solutes which

dissociated, the van’t Hoff factor is applied

to modify m:
T f  K f m 
i
 OSMOSIS: MOLECULAR
DISCRIMINATION
 A semi-permeable membrane
discriminates on the basis of molecular
type
 Solvent molecules pass through
 Large molecules or ions are blocked
 Solvent molecules will pass from a place of
lower solute concentration to higher
concentration to achieve equilibrium
OSMOTIC
PRESSURE
 CALCULATING OSMOTIC
PRESSURE
 The ideal gas law states
PV  nRT
 But n/V = M and so
  MRT
 Where M is the molar concentration of
particles and Π is the osmotic pressure
 Note: molarity is used not molality
 OSMOTIC PRESSURE AND
MOLECULAR
MASS
 Molar mass can be determined using any
of the colligative properties
 Osmotic pressure provides the most
accurate determination because of the
magnitude of Π
 0.0200 M solution of glucose exerts osmotic
pressure of 374 mm Hg (0.5 atm) but freezing
point depression of only 0.02ºC
 DETERMINING
 MOLAR
A solution MASS
contains 20.0 mg insulin in
5.00 ml develops osmotic pressure of 12.5
mm Hg at 300 K 
M
RT
12.5mmHg 1760mmHg
M  6.68104 M
L  atm
0.0821 mol  300K
K
CONVERTING MOLARITY TO
MOLAR MASS:
 Moles insulin = MxV = 3.34x10-6 mol

 Molar mass = mass of insulin/moles of

insulin
= 0.0200 g/3.34x10-6 mol
= 5990
g/mol
 VOLATILE SOLUTE:
TWO LIQUIDS
 Total pressure is the sum of the pressures
of the two components

Ptotal  PA  PB
∘
Ptotal  P X A  PB X B
A
∘
IDEAL BEHAVIOUR OF LIQUID
MIXTURE
 Total pressure in a mixture of toluene (b.p. =

110.6ºC) and benzene (b.p. = 80.1ºC)

equals sum of vapor pressures of
∘
P
components P X
total nP X ∘
ben t
be ol
tol
 DEVIATIONS FROM
IDEAL
 Real solutions can deviate from the ideal:
 Positive (Pvap > ideal) solute-solvent interactions
weaker
 Negative (Pvap < ideal) solute-solvent interactions
stronger
 FRACTIONAL DISTILLATION:
SEPARATION OF LIQUIDS
WITH DIFFERENT BOILING
POINTS
 The vapour above a liquid is richer in the
more volatile component
 Boiling the mixture will give a distillate
more concentrated in the volatile
component
 The residue will be richer in the less
volatile component
 PURIFICATION IN
STAGES
 A 50:50 mixture produces a vapour rich in hexane
 That mixture condensed is about 90:10 hexane
 The 90:10 mixture produces vapour about 95:5
 THE PRACTICE OF FRACTIONAL
DISTILLATION
 In practice, it is not necessary
to do the distillation in
individual steps
 The vapour rising up the
column condenses and re-
evaporates continuously,
progressively becoming
enriched in the volatile
component higher up the tube
 If the column is high enough,
pure liquid will be collected
in the receiver