Mulungushi University

- Pursuing the frontiers of

knowledge

Solutions and their Properties

By A. Mbozi

School Of Science, Engineering

and Technology

1
 Outline
• Colligative Properties of Non- Electrolytes

 Lowering of vapour pressure

 Elevation of boiling point
 Depression of freezing point
 Development of an osmotic pressure
• Colligative Properties of Electrolyte Solutions
 Colligative Properties
On adding a solute to a solvent, the properties of the
solvent are modified.
• Vapor pressure decreases
• Melting point decreases
• Boiling point increases
• Osmosis is possible (osmotic pressure)
These changes are called COLLIGATIVE
PROPERTIES.
They depend only on the NUMBER of solute particles
relative to solvent particles, not on the KIND of
solute particles.
Colligative Properties of Non-Electrolytes

Colligative properties are properties that

depend only on the number of solute
particles in solution and not on the nature
of the solute particles.
– These properties include:
1. Lowering of vapor pressure
2. freezing point depression
3. boiling point elevation
4. osmosis
 1. Lowering of vapour Pressure
Vapor Pressure of a Solution- Definition
Pressure exerted by the gas or vapor released by a liquid or
solid substance in a closed container or space.
 1. Lowering of vapour Pressure
• The vapour pressure of a liquid depends upon the ease
with which the molecules are able to escape from the
surface of the liquid.
• When a solute is dissolved in a solvent, solute molecules
are distributed uniformly throughout the solution with
some of them near the surface of the liquid

• Non volatile solute molecules show no measurable

tendency to escape from the solution at a given
temperature, but like the solvent molecules all around
them, exert a strong inward pull at the surface on those
fast moving molecules of solvent about to escape.
1. Lowering of vapour Pressure
• As a result very few solvent molecules escape
from the surface per second
• Since the rate for return of vapour molecules

to the liquid is unchanged by the presence of

the solute, the pressure set up by the vapours
at equilibrium will be less than would
otherwise
 Chemists have
havebeen the actual
observed thatpressure
the vapor
pressure of a volatile solvent can be reduced by
the addition of a nonvolatile solute.
1. Lowering of vapour Pressure

In Summary:
• The particles of solute are surrounded by and
attracted to particles of solvent.
• Now the solvent particles have less kinetic
energy and tend less to escape into the space
above the liquid.
• So the vapor pressure is less.
1. Lowering of vapour Pressure

• In case of a non-volatile solute, the

relationship between the vapour
pressure of solution and the vapour
pressure of solvent depends on the
concentration of the solute in the
solution.
• This relationship is given by Raoult’s Law.
1. Lowering of vapour Pressure

– In 1886, Francois Marie Raoult observed

that the vapor pressure of a solution
depended on the mole fraction of the
solvent.
1. Lowering of vapour Pressure
Raoult’s Law states that
“the vapour pressure of a solvent over a solution
(Ps) is given by the vapour pressure of the pure
solvent (Po) times the mole fraction of the
solvent (Xsolvent)
o
Psolution  ( Psolvent )( solvent )
where Psolution is the vapor pressure of the
solution, csolvent is the mole fraction of the
solvent, and Posolvent is the pure vapor
pressure of the solvent.
1. Lowering of vapour Pressure
• If a solution contains a volatile solute,
then each component contributes to
the vapor pressure of the solution.
o o
Psolution  ( Psolvent )( solvent )  ( Psolute )( solute )
– In other words, the vapor pressure of the
solution is the sum of the partial vapor
pressures of the solvent and the solute.
– Volatile compounds can be separated
using fractional distillation.
 Sample Question
• Calculate the vapour pressure of a solution made by
dissolving 218 g of glucose (molar mass 180.2 g/mol) in 460
mL of water at 30C.What is the vapour pressure lowering?
The vapour pressure of pure water at 30  C is given as 31.82
mmHg. Assume the density of the solution is 1.00 g/mL.

o
Psolution  ( Psolvent )(  solvent )
Worked Example 12.7
Determination of Molecular Mass from
Lowering of vapour Pressure
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

Determination of Molecular Mass from
Lowering of vapour Pressure

• The molecular mass of a non-volatile solute can

be determined by measuring the lowering of
vapor pressure PO – PS produced by dissolving a
known weight of it in a known weight of the
solvent
• Knowing the experimental value of the lowering
of vapour pressure, and the molecular mass of
the solvent(M), the molecular mass of solute
(m) can be calculated
Determination of Molecular Mass from
Lowering of vapour Pressure

Let’s suppose that w gram of solute is dissolved

in W gram of the solvent. m and M are the
molecular masses of the solute and solvent
respectively.

Moles of solute (n) = wm

Moles of solvent (N) = W/M
Substituting these values in Raoult’s law equation:

Pso ln  Psolv X solute

Po  Ps n

Po n N
Po  Ps w/ m

Po w / m W / M
Knowing the experimental value of the lowering of vapour
pressure, and the molecular mass of the solvent(M), the
molecular mass of solute(m) can be calculated
Determination of Molecular Mass from
Lowering of vapour Pressure

18.2g of urea is dissolved in 100g of water at

50C. The lowering of vapour pressure
produced is 5mm Hg. Calculate the molecular
mass of urea. The vapour pressure of water at
50C is 92 mm Hg.
• Modified Raoult’s Expression:

Po  Ps w/ m

Po w / m W / M
Determination of Molecular Mass from
Lowering of vapour Pressure
- In this case;
w, the weight of solute= 18.2;
the weight of solvent = 100g;
the molecular mass of water = 18 g/mol
The molecular mass of solute = ?
The lowering of vapour pressure,
Po  Ps = 5 mmHg
Po , the vapour pressure of water at
50C = 92 mm Hg
Determination of Molecular Mass from
Lowering of vapour Pressure

Po  Ps n

Po n N
5 18.2 / m

92 18.2 / m  100 / 18
Therefore Molecular Mass of Urea = 57.05 g/mol
Determination of Molecular Mass from
Lowering of vapour Pressure

1. Glycerine, C3H8O3, Is a non-volatile liquid with

a density of 1.26g /mL. Calculate the vapour
pressure at 25C of a solution made by adding
50mL glycerine to 500mL of water. The vapour
pressure of pure water at 25C is 23.8 torr.
Worked Example 12.7
 Boiling-Point Elevation
• Nonvolatile solute elevates the boiling
point of the solvent.
• ΔT = Kbmsolute
ΔT = boiling-point elevation
Kb = molal boiling-point elevation
constant
msolute = molality of solute
Copyright © Cengage Learning. All rights reserved 24
 Boiling Point
• Since adding a solute to water decreases the
vapor pressure, what will happen to the
boiling point?
– It will increase!
– Called boiling-point elevation
 Boiling Point Elevation
• When a liquid is heated, its vapor pressure
rises and when it equals the external (e.g.
atmospheric pressure, the liquid boils.
• We have seen that addition of a non-volatile
solute lowers the vapour pressure of a
solvent, and it will require a higher
temperature before its vapour pressure
becomes 1 atm.
• Consequently, the normal boiling point of the
solution is elevated.
 Boiling Point Elevation

• Nonvolatile solute elevates the boiling

point of the solvent.
• ΔT = Kbmsolute
ΔT = boiling-point elevation
Kb = molal boiling-point elevation
constant
msolute = molality of solute
27
 Magnitude of elevation
• Depends on the number of particles present
• Concentration is measured in molality
(independent of T)
• Kb is the molal boiling point elevation constant
• Note: it is the number of particles

Tb  K b m
 Boiling Point and molecular mass
Tb  K b m
mole( solute ) mass
BUT m mole( solute ) 
kg ( solvent ) molarmass

grams( solute )
m
grams( solvent )
molarmass ( solute ) X
1000 g / kg ( solvent )
• Now if a = mass of solute in grams; b = mass of
solvent in grams; M = molecular mass of
solute, then substituting for molality
1000 XKbXa
Tb 
MXb
1000 XKbXa
M
Tb Xb
 Freezing Point Depression
• The freezing point of a solution is the temperature at
which the liquid and solid phases exist in equilibrium.
• The solvent molecules in a solution are somewhat
more separated from each than they are in the pure
solvent.
• Hence, the temperature of a solution must be lowered
below the freezing of the pure solvent in order to
freeze it.
• The difference of the freezing point of the pure solvent
and the solution is referred to as the depression of
freezing point, and is represented by the symbol, Tf
 Freezing Point Depression

• Presence of solute in
water disrupts the
freezing pattern
• Need to withdraw
MORE energy from a
solution for it to
solidify
– Called freezing-point
depression
 Freezing Point Depression

• When a solute is dissolved in a solvent, the

freezing point of the solution is lower than
that of the pure solvent.
• ΔT = Kfmsolute
ΔT = freezing-point depression
Kf = molal freezing-point depression
constant
msolute= molality of solute

33
 Freezing point and molecular mass

• Like in the case of boiling point elevation;

Molecular mass of a solute (m) is given by;

1000 XKfXa
M
T f Xb
Table of Kb and Kf
 A problem to consider….
An aqueous solution is 0.0222 m in glucose.
What is the boiling point and freezing point
for this solution?
Table 12.3 gives Kb and Kf for water as 0.512 oC/m
and 1.86 oC/m, respectively. Therefore,

ΔT = Kfmsolute ΔT = Kbmsolute

The boiling point of the solution is 100.0114oC and

the freezing point is –0.0413oC.
 Osmotic pressure
• The phenomenon of osmosis depends on the
existence of semi-permeable membranes
• Such membranes are of variety, but they are all
characterised by the fact that they allow one
component of a solution to pass through and
prevent the passage of another component
• 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 molecules passes into more
concentrated 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
PV nRT

V V
• 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

 = MRT
 = osmotic pressure (atm)
M = molarity of the solution
R = gas law constant
T = temperature (Kelvin)

Copyright © Cengage Learning. All rights reserved 40

 Calculating osmotic pressure
• The average osmotic pressure of blood is 7.7
atm at 25 C. Calculate the concentration of
glucose, C6H12O6 in the blood.

  MRT OR M 
RT
7.7 atm
M
0.0821L.atm / K .molX 298 K

M  0.31M
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
 Determining molar mass
• A solution containing 20.0 mg insulin in 5.00
ml develops an osmotic pressure of 12.5 mm
Hg at 300 K. Calculate the molar mass of
insulin. 
M
RT
12.5mmHgX 1atm
760mmHg
M  6.68  10  4 M
L  atm
0.0821 X 300 K
mol  K
 Determining molar mass
• Moles insulin = MxV
= 6.68 x 10-4 mol/L x 0.005 L
= 3.34x10-6 mol
• Molar mass = mass of insulin moles of insulin
= 0.0200 g 3.34x10-6 mol
= 5990 g/mol
 Colligative Properties of Electrolyte
Solutions
• The colligative properties of non-Electrolyte solutions
viz, vapour pressure lowering, boiling point elevation,
freezing point depression and osmotic pressure, all
depend upon the total number of solute particles
present in the solution.
• In case of electrolyte solutions various electrolytes
ionise and give more than one ion per formula unit in
the solution.
• Therefore the colligative effect of an electrolyte
solution is greater than that of a non electrolyte
solution of the same molal concentration.
 Colligative Properties of Electrolyte
Solutions
• The colligative properties of an electrolyte solution
can be expressed by means of the same relation as
for non electrolytes, by introducing a factor i, which
is known as van’t Hoff factor .
• This factor gives a measurement of the extent to
which electrolytes dissociate..
• Thus the van’t Hoff factor can be defined as “the
ratio of the colligative property of an eletrolyte
solution to the corresponding property of an no-
electrolyte solution”.
 Colligative Properties of Electrolyte
Solutions
• Therefore for electrolyte solutions, the following equations apply:

Δ T = Kf m i Δ T = Kb m i
Kb and Kf = (called the boiling-point-elevation
constant and freezing point constant
respectively), depends only on the solvent
m = molal concentration of the solution
i = number or parts the solute breaks into
  iMRT
Colligative Properties of Electrolyte
Solutions

1000 XKbXa
M  iX
Tb Xb
1000 XKfXa
M  iX
T f Xb
 Relationship between van’t Hoff factor
and degree of dissociation
• Since colligative properties depend on the
number of particles in solution, the van’t Hoff
factor may be given as
 Relationship between van’t Hoff factor
and degree of dissociation
The degree of dissociation is the fraction of an
electrolyte which is dissociated into ions in
aqueous solution. It is usually represented by .
E.g , if an electrolyte is 50% dissociated, its degree
of dissociation,  is 0.5.

Where n is number of ions

i is the van’t Hoff factor
 is the degree of dissociation