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Colligative Properties: Vapour Pressure Boiling Point Freezing Point Osmotic Pressure

Colligative properties depend only on the number of solute particles and not on the chemical identity of the solute. The four main colligative properties are vapor pressure lowering, boiling point elevation, freezing point depression, and osmotic pressure. Raoult's law can be used to predict vapor pressure lowering in solutions containing nonvolatile solutes. The magnitude of boiling point elevation and freezing point depression depends on the molality of solute particles. Osmotic pressure can be used to determine the molar mass of a solute.

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Naman Gupta
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93 views

Colligative Properties: Vapour Pressure Boiling Point Freezing Point Osmotic Pressure

Colligative properties depend only on the number of solute particles and not on the chemical identity of the solute. The four main colligative properties are vapor pressure lowering, boiling point elevation, freezing point depression, and osmotic pressure. Raoult's law can be used to predict vapor pressure lowering in solutions containing nonvolatile solutes. The magnitude of boiling point elevation and freezing point depression depends on the molality of solute particles. Osmotic pressure can be used to determine the molar mass of a solute.

Uploaded by

Naman Gupta
Copyright
© © All Rights Reserved
Available Formats
Download as DOCX, PDF, TXT or read online on Scribd
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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

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