Colligative Properties

Those properties which depend on the number of solute particles (molecules,atoms or ions) but not upon
their nature are called colligative properties. The following are the colligative properties:
(a) Relative lowering of vapour pressure of the solvent,
(b) Elevation of boiling point of the solvent,
(c) Depression of freezing point of the solvent,
(d) Osmotic pressure of the solution.
(a) Relative lowering of vapour pressure: The addition of a non-volatile solute to a volatile solvent
decreases the escaping tendency of the solvent molecules from the surface of solutions as some of
the surface area is occupied by non-volatile solute particles. According to Raoult's law, the relative
lowering of vapour pressure is equal to mole fraction of solute.
P-P
Thus, = XB =
PA
For a dilute solution, ng << n4, hence neglecting n,in the denominator, we have
P-P W; XM,
M,XW,
W, XM,
M_ =
Pi-p W,
(b) Elevation of boiling point: Boiling point is Boiling point of
the temperature at which the vapour pressure Solyent Solution
of a liquid becomes equal to the atmospheric 1atm
pressure. When a non-volatile solute is added
Solven
Solutior
to a volatile solvent, the vapour pressure of the Vapour
pressure
(atm)
solvent decreases. In order to make this solution
boil its vapour pressure must be increased by
raising the temperature above the boiling point
of the pure solvent. The difference in the boiling
point of solution (T) and that of pure solvent AT,
(T;) is called elevation of boiling point (AT,).
Thus,
Elevation of boiling point = AT, = T, - T
(Fig. 1.4)
the Temperature (K)
For dilute solution, it has been found that
Fig. 1.4: Vapour pressure temperature
elevation of boiling point is directly proportional
the curves showing elevation in
solute in
to the molal concentration of the boiling point of solution
solution. Thus,
AT, c mn or AT,= K, m
where K, is a constant called molal elevation constant or ebullioscopic constant.
When m=lmol kg, AT, = K,
Hence. molal elevation constant may be defined as the elevation in boiling point when one mole of a
non-volatile solute is dissolved in one kilogram (1000 g) of solvent. The unit of K, is Kkg mol
W,B X1000
As m=
Mg X W,A
 K, XW, x 1000
Therefore, AT, =
M,X WA
K, XW X1000
Mg= AT, XW,
(c) Depression of freezing point: Freezing point is defined as Liquid
solvent

the temperature at which the vapour pressure of a substance

in its liquid phase is equal to its vapour pressure in the solid Vapour
pressure
(atm) Solution

phase. A solution freezes when its vapour pressure equals

the vapour pressure of the pure solid solvent. Whenever FrozeY-so

a non-volatile solute is added to the volatile solvent its

vapour pressure decreases and it would become equal to
that of solid solvent at a lower temperature. The difference
in the freezing point of pure solvent (T) and that of the
solution (T) is known as depression of freezing point
(AT). Thus,
T:
Depression of freezing point =AT, =T-T;. Temperature (K)
It has been found that for a dilute solution, depression in Fig. 1.5: Vapour pressure temperature
freezing is directly proportional to molality of the solution. curves showing depression in
freezing point of solution
AT,c mor AT;= K;m
where K_is a constant called molal depression constant or cryoscopic constant.
When m=1 mol kg, AT,= K,
Hence, molal depression constant may be defined as the depression in freezing point when one mole
of non-volatile solute is dissolved in one kilogram (1000 g) of solvent. The unit of K, is Kkg mol',
W, X1000
Since, m=
M, XW,
K, X
W, X1000
AT;= M, XW,
K, XWx 1000
or, M =
AT, XW,
The values of K, and K which depend upon the nature of the solvent and concentration of the solution,
can be ascertained from the following relations:
RX M,X(T)
K, = HX1000

RX M,X(T)
K,= AHX 1000
fus

where, R=Universal gas constant

M= Molecular mass of solvent
T = Boiling point of pure solvent
Ayap H = Enthalpy of vapourisation of solvent
T? = Freezing point of pure solvent
= Enthalpy of fusion of solid solvent
(d) Osmosis: When a solution is separated from its solvent by a
is a spontaneous flow of solvent molecules from solvent
semipermeable membrane (SPM) there
compartment to solution compartment.
The phenomenon is called osmosis. This movement of solvent is only in one direction. In
diffusion,
however, movement takes place in both the directions.
Semipermeable membrane (SPM): A membrane through which only solvent molecules can pass but
not the solute ones. Cellophane, parchment paper and the wall of living cell are the
It is also made of inorganic material, copper examples of SPM.
ferrocyanide [Cu,[Fe(CN)6l].
Osmotic pressure (): The osmotic pressure of a
solution is the exXcess pressure that must be applied to I= hpg
a solution to prevent osmosis, i.e., to
stop the passage
of solvent molecules into it through
membrane (Fig. 1.6).
semipermeable
-Solvent
Osmotic pressure (Tr) is proportional to molarity (C)
of the solution at a given temperature T. Thus, Solution
T = CRT
W, XRXT Semipermeable
Or, Tt = PRT membrane
M, XV
W, XRXT Fig. 1.6:The principle of measuring osmotic
Or, M_ = pressure: The pressure in excess of atmospheric
pressure that must be applied to the solution to
prevent it from rising in the tube is the osmotic
Reverse osmosis: If a pressure larger than the pressure. This will also be equal to hydrostatic
Osmotic pressure is applied to the solution side, the pressure of the liquid column of height, h.
pure solvent (or water) flows out of the solution
through the semipermeable membrane. In this Piston
way the direction of osmosis is reversed and so Pressure >1
the process is called reverse osmosis (Fig. 1.7).
Thus, we can say that reverse oSmosis is Fresh water Salt water

just opposite to the osmosis when an extra

pressure is applied. Reverse osmosis is used in Water
SPM
desalination to get pure water from sea water. outlet

Fig. 1.7: Reverse osmosis occurs when a pressure

Isotonic solutions: Two solutions are said to larger than the osmotic pressure is
be isotonic when they exert the same
osmotic applied to the solution
molar
pressure because they have the same
with body fluids.
concentration. AIl intravenous injections must be isotonic
membrane. no
Isosmotic soButions: When two isotonic solutions are separated by a semipermeable
calledisosmotic solutions.
Osmosis occurs. The solutions are
solution is said to be
Hvpotonic solutions: A solution having lower osmotic pressure than the other
solution.
hypotonic with respect to the other
solution is said to be
Hypertonic solution: A solution having higher osmotic pressure than the other
solution.
hypertonic with respect to other
Plasmolysis: When the cell is placed in a hypertonic soluion, the fiuid comes out of the cell due to
osmosis and as a result cell material shrinks gradually. This process is called plasmovsis
7. Abnormal Molar Masses
Association: Association of molecules leads to decrease in the number of particles in the solution
resulting in a decrease in the value of colligative property. As colligative property is inversely related
to the molecular mass. Therefore, higher value is obtained for molecular mass than normal values.
 For example, when ethanoic acid is dissolved in benzene it undergoes dimerisation and shows a
molecular mass of 120(normal molecular mass is 60).

2CH;COOH
Benzene
HC-e -CH,
O-H----0

Dissociation: Dissociation leads toincrease in the number of solute particles in the solution resulting
inan increase in the value of colligative property. Since colligative property is inversely related to the
molecular mass, therefore, molecular mass of such a substance ascalculated from colligative property
will be less than its normal value. For example, KCl is an electrolyte. When it is dissolved in water i
dissociates into K and CI ions and there would be double the number of particles if complete
74.5
dissociation takes place. Hence, it is expected to have molecular mass 37.25 g or g.
2

KCI K + CIr
van't Hoff Factor (): It may be defined as the ratio of normal molecular mass to the observed
molecular mass of the solute.
Normal molecular mass
i=
Observed molecular mass

Or, i=
Observed colligative property
Calculated value of colligative property
Total number of moles of particles after association/dissociation
Or, i=
Number of particles before association/dissociation
van't Hoff factor (i) expresses the extent of association or dissociation of the solute particles in the
solutions.

In case of association, i<1

In case of dissociation, i >1
When there is neither association nor dissociation, i= 1
8. Modified Form of Colligative Properties
Inclusion of ? modifies the equation for colligative properties as follows:
Relative lowering of vapour pressure of solvent
PA- PA =i nB
PA n
Elevation of boiling point, AT, = iky m
Depression of freezing point, AT,=iKçm
Osmoticpressure, Tt =iCRT