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
 Vapor Pressure Lowering
- the pressure exerted by a vapor in
equilibrium with its liquid.
If a solute is non-volatile, non electrolyte
and is mixed with a volatile solvent, the
vapor pressure of this solution is less than
the pure volatile solvent.
 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

 Raoult’s Law
 If a solution contains only one solute, the
mole fraction of the solvent (X1) is
calculated using the equation:
X1 = 1-X2
Where:
X2 = mole fraction of solute.
Eq 1. can also be written as
P2 = (1-X2) P1
 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
VAPOR PRESSURE OF SOLVENT (P1) vs. MOLE
FRACTION OF SOLVENT (X1)
 SAMPLE PROBLEM:
1. Methyl alcohol, CH3OH and ethyl alcohol,
C2H5OH form ideal solutions. At 50°C, the
vapor pressure of pure methyl alcohol is
0.529 atm, and the vapor pressure of pure
ethyl alcohol is 0.292 atm. What is the vapor
pressure at 50°C of a solution containing 24
g of methyl alcohol and 5.76 g of ethyl
alcohol?
 SAMPLE PROBLEM:

2. A solution prepared from 196 g of a

nonvolatile, non dissociating solute in 5
mole of water has a vapor pressure of 0.312
atm at 75°C. What is the molecular weight
of the solute? The vapor pressure of pure
water at 75°C is 0.380 atm.
 SAMPLE PROBLEM:

3. A solution containing 1 mol of acetone

and 1.50 mol of chloroform has a vapor
pressure of 0.329 atm at 35°C. at this
temperature, the vapor pressure of acetone
is 0.453 atm and the vapor pressure of pure
chloroform is 0.388 atm. What would the
vapor pressure of this solution be if the
components formed ideal solutions?
 SAMPLE PROBLEM:

4. Calculate the mass of propylene glycol,

C3H8O2, that must be added to 0.500 kg of
water to reduce the vapor pressure by 4.60
torr at 40°C if the vapor pressure of water
at 40°C is 55.3 torr.
 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
 SAMPLE PROBLEMS
 Calculate the boiling point of a 20 percent
aqueous sucrose (C12H22O11) solution.

 What is the boiling point of a solution that

contains 12.5g biphenyl, C12H10 in 100g of
bromobenzene? The normal boiling point of
bromobenzene is 156.0°c Kb for
bromobenzene is +6.26°c/m.
 SAMPLE PROBLEMS
 Carbon disulfide, CS2, boils at 46.30°c and has a
density of 1.261g/ml.
 A) when 0.250mol of nondissociating solute is
dissolve in 400 ml of CS2, the solution boils at
47.46°c, what is the molal boiling point elevation
constant for CS2?
 B) when 5.39g of nondissociating unknown is
dissolve in 50.0ml of CS2, the solution boils at
47.08°c. What is the MW of the unknown
 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
 SAMPLE PROBLEMS
 Calculate the freezing point of a solution
containing 0.600kg CHCl3 and 42.0g of
eucalyptol, C10H18O, a fragrant substance
found in the leaves of eucalyptol trees. (Kf
chloroform CHCl13, is 4.68°c/m) (Nf pt.= -
63.5°c)
 SAMPLE PROBLEMS
 How many grams of glucose, C6H12O6 (a
nondissociating solute) are required to lower the
freezing point of 150g of H2O by 0.750°c?

 A solution that contains 13.2g of solute is 250g

of CCl4 freezes at -33.0°c. What is the MW of the
solute? The normal freezing point of CCl4 is -
28.8°c and Kf is 29.8°c/m?
 SAMPLE PROBLEMS
 A solution that contains 14.8g of
naphthalene, C10H8 in 300g of
nitrobenzene freezes at 3.0°c. The normal
freezing point of nitrobenzene is 5.70°c.
What is the freezing point constant, Kf for
nitrobenzene?
 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
 SAMPLE PROBLEM
 What is the osmotic pressure at 20°c of a
0.0020 M sucrose, C12H22O11 solution?

 An aqueous solution that contains 0.157g

penicillin G in 100ml of solution has an
osmotic pressure of 0.115 atm at 25°c.
What is MW of penicillin G?
 The molecular weight of codeine is 3.17.
The osmotic pressure of a saturated
solution of codeine in water is 0.641 atm at
25°c.
 A) How many grams of codeine are
dissolve in one liter of the saturated
solution?
 B) what is the molarity of solution?
 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