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Colligative Properties

Vapour pressure
Boiling point
Freezing point
Osmotic pressure

Learning objectives

Describe meaning of colligative property

Use Raoults law to determine vapor pressure of
Describe physical basis for vapor pressure
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 dont 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

Non-volatile solutes and Raoults law

Vapor pressure of solvent in solution containing nonvolatile 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 Raoults law:

Boiling point elevation

In solution vapor
pressure is reduced
compared to pure
Liquid boils when
vapor pressure =
atmospheric pressure
Must increase T to
make vapor pressure
= atmospheric

Molecular view of Raoults 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

Raoults 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

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, Raoults 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
Vant 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
Freezing point depression

Pure solid separates out at

freezing negative Tf

Boiling point elevation

Vapour pressure in solution is

lower, so higher temperature
is required to reach
atmospheric positive Tb

Magnitude of elevation

Depends on the number of particles

Concentration is measured in molality
(independent of T) T K m
Kb is the molal boiling point elevation
Note: molality is calculated in terms of


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 vant 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

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 required to prevent transport equals

osmotic pressure

Calculating osmotic pressure

The ideal gas law states


But n/V = M and so


Where M is the molar concentration of

particles and is the osmotic pressure
Note: molarity is used not molality

Osmotic pressure and molecular


Molar mass can be determined using any

of the colligative properties
Osmotic pressure provides the most
accurate determination because of the
magnitude of

0.0200 M solution of glucose exerts osmotic

pressure of 374 mm Hg (0.5 atm) but freezing
point depression of only 0.02C

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

12.5mmHg 1


6.68 104 M
L atm
mol K

Converting molarity to molar mass:

Moles insulin = MxV = 3.34x10-6 mol

Molar mass = mass of insulin/moles of
= 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

Ideal behaviour of liquid mixture

Total pressure in a mixture of toluene (b.p. =

110.6C) and benzene (b.p. = 80.1C) equals
sum of vapor pressures of components

Ptotal P X ben P X tol



Deviations from ideal

Real solutions can deviate from the ideal:

Positive (Pvap > ideal) solute-solvent interactions

Negative (Pvap < ideal) solute-solvent interactions

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
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 reevaporates 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