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
Colligative properties for nonvolatile
solutes:
Take it to the bank
 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
 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
 Raoult’s Law
 Vapor pressure above solution is vapor
pressure of solvent times mole fraction of
solvent in solution
Pso ln  Psolv X solv
 Vapour pressure lowering follows:

Pso ln  Psolv X solute

 Counting sheep (particles)
 The influence of the solute depends only on the
number of particles
 Molecular and ionic compounds will produce
different numbers of particles per mole of
substance
 1 mole of a molecular solid → 1 mole of particles
 1 mole of NaCl → 2 moles of particles
 1 mole of CaCl2 → 3 moles of particles
 Solution Deviants
 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 dissolved
 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 molality
(independent of T) T  K m
b b
 Kb is the molal boiling point elevation
constant
 Note: it is the number 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
 For solutes which are not completely
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
 Solvent passes into more conc solution
increasing its volume
 The passage of the solvent can be
prevented by application of a pressure
 The pressure to prevent transport is the
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 computed from 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 an
osmotic pressure of 374.2 mm Hg but a
freezing point depression of only 0.02ºC
 Determining molar mass
 A solution contains 20.0 mg insulin in
5.00 ml develops an osmotic pressure of
12.5 mm Hg at 300 K 
M
RT
12.5mmHg 1
760mmHg
M  6.68 10  4 M
L  atm
0.0821 300 K
mol  K
 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  P X B

A

B
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
components

Ptotal  P X ben  P X tol


ben

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 with a
71:29 composition
 That mixture boiled produces a vapour
with a 86:14 composition
 That mixture boiled produces a vapour
with a composition 94:6
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