By: Noha Fathy El Azab, PhD.

Lecturer of Pharmaceutical Analytical Chemistry1

 Colligative Properties of Solutions
• Colligative properties are properties of solutions that
depend upon the ratio of the number of solute particles to
the number of solvent molecules in a solution, and not on
the type of chemical species present.
• Here we consider only those properties which result because
of the dissolution of nonvolatile solute in a volatile liquid
solvent. They are independent of the nature of the solute
because they are essentially due to the dilution of the
solvent by the solute.
• The word colligative is derived from the Latin “colligatus”
meaning bound together.
• These properties are helpful in the determination of
molecular weight of the dissolved substances which are 2
non-volatile.
• Among colligative properties are:
Vapour pressure lowering
Boiling point elevation
Freezing point depression
Osmotic pressure

3
 1. Vapour Pressure Lowering
• A solvent in a closed container reaches a
state of dynamic equilibrium.
• The pressure exerted by the vapour in the
headspace is referred to as the vapour
pressure of the solvent.
• The addition of any nonvolatile solute (one
with no measurable vapor pressure) to any
solvent reduces the vapour pressure of the
solvent.
• Solute-solvent interactions contribute to
this effect.
• Therefore, the vapour pressure of a
solution is lower than that of the pure
solvent.
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 1. Vapour Pressure Lowering
• Nonvolatile solutes
reduce the tendency
of the surface solvent
molecules to escape
the liquid as some of the
area is occupied by
non volatile solute.

• The extent of vapour

pressure lowering
depends on the
amount of solute.
• Raoult’s Law quantifies
the amount of vapour
pressure lowering that is observed.
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 1. Vapour Pressure Lowering
• Raoult’s Law:
PA = XAPOA

where PA = partial pressure of the solvent (A)

vapour above the solution (ie with the solute)
XA = mole fraction of the solvent (A)
PoA = vapour pressure of the pure solvent (A)
XA+XB=1
XA= 1-XB
PA = (1-XB )POA
POA- PA =P⁰AXB Relative vapour pressure lowering

POA- PA ΔP nB
= = XB =
P⁰A P⁰A nA+nB 6
PRACTICE EXERCISE
The vapour pressure of pure water at 110°C is 1070 torr. A solution of
ethylene glycol and water has a vapour pressure of 1.00 atm at 110°C.
Assuming that Raoult’s law is obeyed, what is the mole fraction of
ethylene glycol in the solution?
1 torr=0.0013 atm

Vp of pure water=1070 torr=1.39 atm

Δp/po=XB
XB=0.39/1.39=0.28

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 2. Boiling Point Elevation
• Boiling point is the
temperature at which the
vapour pressure above the
liquid becomes equal to an
external pressure of 760 mm
Hg.
• The addition of a nonvolatile
solute causes solutions to
have higher boiling points
than the pure solvent owing
to the fact that the solute
lowers the vapour pressure
of the solvent.
• Higher temperature is
needed to boil in order for
vapour pressure to equal 1
atm.
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 Boiling Point Elevation and Freezing Point Depression
(Vapour pressure temperature curve)

Solid line curve represents the variation of vp of pure solvent with

temp.
And the same for solution curve.
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 2. Boiling Point Elevation
Bp elevation= T - To = DTb.

DTb
=K constant
Dp
DTb= K Dp
Po Po
DTb= K.X2
Po

DTb = Po.X2.K
W2 M1
= Po × × .K’
W1 M2 10
DTb = Po .M1.k. W2
M2 × W1
W2
DTb =k’ ×1000/1000
M2 × W1
= k’ W2
× × 1000
1000 M2 × W1

W2
× 1000 = m
M2 × W1

DTb = k’ × m
1000 11
• The change in boiling point is proportional to the number of solute
particles present and can be related to the molality of the solution:

DTb = Kb.m
where DTb = boiling point elevation
Kb = molal boiling point elevation constant
m = molality of solution
The value of Kb depends only on the identity of the solvent.

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 Determination of Boiling Point Elevation
Landsberger’s
apparatus
a) Boiling flask:-
• Flask contains pure solvent
which is heated and solvent
vapours are sent to boiling
tube.
b) Boiling tube:-
• It has a bulb with a hole in the side
tube . d) Outer Jacket :-
• It is fitted with a delivery tube The boiling tube is surrounded by a
c) Beckmann thermometer:- jacket. It collects the uncondensed
very sensitive, measures small hot vapours coming from the
differences in temperature up to boiling tube through the hole.
0.01 0 C. These vapours are led to a
13
condenser.
 Practical uses for Boiling Point elevation
Phenomenon:
Salt in water when cooking
pasta.
Salt in pasta water makes it boil
hotter and cooks the pasta faster.
Salt lowers the vapour pressure
which directly affects the boiling
point.

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 2. Boiling Point Elevation

Example: A solution containing 4.5 g of glycerol, a

nonvolatile nonelectrolyte, in 100.0 g of ethanol
has a boiling point of 79.0oC. If the normal BP of
ethanol is 78.4oC, calculate the molar mass of
glycerol. (Ans=92 g/mol)
Given: DTb =
mass solute =
mass solvent =
Kb = 1.22oC/m

Find: molar mass (g/mol) 16

 3. Freezing Point Depression
• A liquid freezes when its particles do not have
enough kinetic energy to overcome the
intermolecular forces between them.
• So the molecules are pulled closer together and
take on a defined shape. When a solute is added,
the freezing point is driven lower – WHY?
• The solute molecules get in the way and make it
harder for the solvent molecules to move closer
and become a solid.

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 3. Freezing Point Depression
• At the freezing point, Solid
and liquid phases are in
equilibrium under a
pressure of 1 atm.
• Equilibrium line rises
vertically from the triple
point, which is lower than
that of pure solvent.

• On addition of a nonvolatile
solute …vapour pressure of the
liquid solvent is lowered … temp.
must drop in order to reestablish
equilibrium between liquid and
solid………solutions have lower
freezing points than the pure 18
solvent.
 3. Freezing Point Depression
• Similar to Boiling Point Elevation, The magnitude of the
freezing point depression is proportional to the number of
solute particles and can be related to the molality of the
solution.
DTf = Kf  m
where DTf = freezing point depression
Kf = molal freezing point depression constant
m = molality of solution

The value of Kf depends only on the identity of the solvent.

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 Determination of Freezing Point Depression
The Beckmann method.
• Freezing tube has side arm (solute
can be introduced), Beckmann
thermometer and a stirrer.

• To prevent rapid cooling of the

contents of the freezing tube, an
outer tube surrounds the freezing
tube so that there is an air space.

• This assembly is placed in a wide

vessel which contains a freezing
mixture maintaining a low
temperature around 5˚C below the
freezing point of the pure solvent.
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 Practical uses for Freezing Point Depression
Phenomenon:
• This phenomenon is what
causes sea water, to remain
liquid at temperatures below
0 °C.
• The radiator fluid in an
automobile is a mixture of water
and ethylene glycol (organic liquid
called antifreeze). It elevates the
boiling point of water , so prevent
it from boiling over in summer
and at the same time depress the
freezing point of the same water
to prevent freeze up in winter
(unless it is extremely cold, e.g.
−30 to −40 °C). 23
• Road salting lower the
freezing point of the ice. It
is placed on by interrupting
the ice crystal formation, it
has to get colder to freeze
salt water.
This allows the street ice to
melt at lower temperatures,
preventing the accumulation
of dangerous, slippery ice.

Commonly used sodium chloride can depress the freezing point of

water to about −21 °C.

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Calculate the boiling and freezing points of an
aqueous solution containing 39.5 g ethylene glycol,
HOCH2CH2OH, dissolved in 750 ml water.
Assume the density of water to be 1.00 g/ml;
its Kb= 0.52 ⁰C Kg mol -1 and Kf = 1.86 ⁰C Kg mol -1

Answer:
Boiling point of solution = 100.44 ⁰ C
Freezing point of solution = -1.58 ⁰ C

27
 4.Osmosis
• Osmosis: the net
movement of a
solvent through a
semipermeable
membrane toward
the solution with
greater solute
concentration to
equalize the solute
concentrations on
the two sides.
• In osmosis, there is net movement of solvent from the
area of lower solute concentration to the area of
higher solute concentration. 28
 4.Osmosis
• Movement of solvent only takes place from high solvent
concentration to low solvent concentration.
• The movement takes place due to the osmotic gradient
created by difference in concentration of the solutions on
both sides of the membrane and the end result is a state
where osmotic equilibrium is reached where movement of
the fluid ceases.
• If the osmotic pressure is the same on both sides of a
semipermeable membrane (i.e., the concentrations are the
same), the solutions are isotonic… no net movement of
solvent occurs.
• Types of Semipermeable membranes : animal membrane,
cellulose membrane and a film of cupric ferrocyanide. The
29
membrane used depends on nature of solute and solvent.
• An inverted thistle funnel, its
end is tied by an animal
membrane, is partially filled
with a concentrated solution
of sugar.
• This is immersed in a beaker
containing pure water.
• Due to osmosis, water will
begin to pass through the
membrane and the level of the
sugar solution in the tube Semipermeable
begins to rise until it reaches a membrane
definite height, depending on
the concentration of the
solution.
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• The hydrostatic pressure set up from the difference in levels of the
sugar solution and pure water surface is the osmotic pressure of
solution.
• “It is the mechanical pressure which must be applied on solution to
prevent the passage of solvent into the solution through semi-
permeable membrane”.

31
 Measurement of osmotic pressure
Frazer and Morse method
• The method employs a porous vessel ,A, in
the walls of which is deposited a layer of copper
ferrocyanide.
• This is connected to a tube B. Both the vessel
and the tube are filled with the solvent.
• The vessel is surrounded by a solution
contained in the bronze cylinder C.
• Solvent will enter the solution and result in
the hydrostatic pressure equal to osmotic
pressure in the vessel C.
• This can be measured by a manometer
attached to C.

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Berkley and Hartley
method.
• The solvent is placed in the
horizontal tube A, on the sides
of which a thin layer of copper
ferrocyanide is deposited.
• The solvent is added to A
through E.
• This tube , A, is placed into a metal jacket B which contains the
solution and carries an attachment C through which pressure can
be applied.
• A is first filled with the solvent through E up to a definite point in
the capillary D. As the result of osmosis, the level of liquid in the
capillary will fall but by applying pressure through C, it is restored
to its initial value.
• This pressure is the osmotic pressure of the solution (). 33
 Van’t Hoff Equation
• The pressure required to stop osmosis, known as osmotic
pressure, , is directly proportional to concentration.
 C (at constant T)
 1 (C  1/V)
V
 V=constant
 T (at constant C)
 V=RT
n
 = ( )RT = MRT
Where
V
V : volume of solution containing 1 mole of solute
R : Universal gas constant
M: molarity of the solution
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n : no of moles of solute
 Applications of Osmosis
Reverse Osmosis:
A Technique for purifying water, in which pressure (larger than the
osmotic pressure) is applied to force the liquid through a
semipermeable membrane in the opposite direction to that in
normal osmosis. Ex. Desalination

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 Applications of Osmosis
Osmosis plays an important
role in living systems:
• Membranes of RBCs are
semipermeable.
• Placing an RBC in a hypertonic
solution (solute concentration
outside the cell is greater than
inside the cell) causes water to
flow out of the cell in a process
called crenation.
• Placing an RBC in a hypotonic solution (solute concentration
outside the cell is less than that inside the cell) causes water to
flow into the cell….The cell ruptures in a process called hemolysis.
36
 Applications of Osmosis

When your hands are immersed

in water for a long time, your skin
looks bloated. This is an effect of
osmosis.

Eating large quantities

of salty food causes
retention of water and
swelling of tissues
(edema).
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 Applications of Osmosis
Other everyday examples of
osmosis:
• A cucumber placed in
brine solution loses
water and becomes a
pickle.

• Prunes expand when

soaked in water
because water
enters by osmosis.

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 Applications of Osmosis
• Osmosis plays a
very important
role in human life
as it helps in the
proper
functioning of
the kidneys.
• Dirty blood is
taken from a
vessel in the arm
and pumped into
a machine.

• Inside the machine, separated by a semipermeable membrane, the

blood flows in the opposite direction to the dialysis fluid, allowing
exchange to occur between the two where a concentration gradient 39
exists.
 Electrolytes
• Solutions of electrolytes: solutes tend to
dissociate into ions so inc. no of particles, so all
colligative prop. become higher.
• Van’t Hoff factor accounts for this
i = colligative effect produced by a definite conc.of electrolyte
The effect observed for the same conc of non electrolyte

Δ P= 𝑖 (Δ P) 0 =i.P0 XB
Δ Tf= 𝑖 (Δ Tf) 0 =i.Kf m
Δ Tb= 𝑖 (Δ Tb)0 =i.Kb m
𝜋 = 𝑖(𝜋) 0 = i.nRT/V
Electrolytes
Problem:
KBr is 79 percent dissociated in solution what is the freezing point
of 0.5 molal solution?
( Kf = 1.85 ⁰ C Kg mol -1 )
Answer:
α= 0.79
And n = X+ Y=2
So i= 1.79
Δ Tf = 1.66 ⁰C
Problem:
0.1 molal solution of acetic acid in water freezes at 0.19 ⁰C.
calculate percentage dissociation of acetic acid at this
temperature?, ( Kf = 1.85 ⁰ C Kg mol -1 ) Ans=2.7 %
44