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
Psoln  Psolv X solv
Vapour pressure lowering follows:

Psoln  PsolvXsolute
 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: 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

Tf  K f m
 For solutes which are not completely
dissociated, the van’t Hoff factor is applied
to modify m:
Tf  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 volume
Passage of solvent can be prevented by applying
pressure
Pressure required to prevent transport equals
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 mass
A solution 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
4
M L  atm  6.6810 M
0.0821 300K
mol  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  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  Pben

Xben  P 
tol Xtol
 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