Colligative Properties

SEMESTRAL REPORT

Nanda Kishore S | DC-II Physics| july-4-2019

Introduction
A solution is a special type of
homogeneous mixture composed of two or more substances.
In such a mixture, a solute is a substance dissolved in another
substance, known as a solvent. The mixing process of a
solution happens at a scale where the effects of chemical
polarity are involved, resulting in interactions that are specific
to solvation. The solution assumes the phase of the solvent
when the solvent is the larger fraction of the mixture, as is
commonly the case. The concentration of a solute in a solution
is the mass of that solute expressed as a percentage of the
mass of the whole solution. Physical properties can be divided
into two categories. Extensive properties (such as mass and
volume) depend on the size of the sample. Intensive properties
(such as density and concentration) are characteristic
properties of the substance; they do not depend on the size of
the sample being studied. The third category that is a subset
of the intensive properties of a system. This third category,
known as colligative properties. Colligative properties are
properties of solutions that depend on the ratio of the number
of solute particles to the number of solvent molecules in a
solution, and not on the nature of the chemical or the identity
of the solute. Colligative properties include,

i) Depression of vapor pressure

ii) Elevation of boiling point
iii) Depression of Freezing point
iv) Osmotic pressure.

Depression of Vapor Pressure

When the temperature of a liquid is below
its boiling point, we can assume that the only molecules that
can escape from the liquid to form a gas are those that lie near

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the surface of the liquid. When a non-volatile solute is added
to the solvent, some of the solute molecules reside in the
space near the surface of the liquid. When a solute is dissolved
in a solvent, the number of solvent
molecules near the surface
decreases, and the vapor pressure
of the solvent drops. This has no
effect on the rate at which solvent
molecules in the gas phase
condense to form a liquid. But it
decreases the rate at which the solvent molecules in the liquid
can escape into the gas phase. As a result, the vapor pressure
of the solvent escaping from a solution should be smaller than
the vapor pressure of the pure solvent. The vapor pressure of a
solution is equal to the mole fraction of the solvent times the
vapor pressure of the pure liquid.

P = solvent Po
This equation, is known as Raoult's law, When the solvent is
pure, and the mole fraction of the solvent is equal to 1, P is
equal to Po. As the mole fraction of the solvent becomes
smaller, the vapor pressure of the solvent escaping from the
solution also becomes smaller.

Raoult's law suggests that the

difference between the vapor pressure of the pure solvent and
the solution increases as the mole fraction of the solvent
decreases. If it depends on the mole fraction of the solute,
then it must depend on the ratio of the number of particles of
solute to solvent in the solution but not the identity of the
solute. The change in the vapor pressure that occurs when a
solute is added to a solvent is therefore a colligative property.

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Elevation of Boiling Point
The boiling point of a liquid at a
given external pressure is the temperature at which the vapor
pressure of the liquid equals the external pressure. The normal
boiling point is the boiling point at a pressure equal to 1 atm.
Addition of solutes to a solvent can lower its vapor pressure.
The vapor pressure has to be raised in order to reach the
boiling point, this means that more energy has to be supplies
to reach the same vapor pressure. Input of more energy
equates to the input of heat in this type of system, so the
boiling point temperature must be higher to obtain the same
vapor pressure. Adding a non-volatile solute to a solution
therefore raises the boiling point of that solution.

The boiling point of the solution is raised according to the

equation

T = i Kb m

T – Change in temperature

i - the van't Hoff factor

Kb - The molal boiling point constant(ebullioscopic constant)

m –Molality

Depression of Freezing Point

The normal freezing point of a liquid is is
the temperature at which a liquid becomes a solid at 1 atm. It
is the temperature at which solid and liquid phases coexist in
equilibrium. As the temperature lowers, the solution becomes
more ordered as it moves toward the solid phase. At freezing
point liquid solvent and solid solvent are at equilibrium, so that
their vapor pressures are equal. When a non-volatile solute is
added to a volatile liquid solvent, the solution vapor pressure
will be lower than that of the pure solvent. As a result, the solid

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will reach equilibrium with the solution at a lower temperature
than with the pure solvent.
T =-i Kfm

T – Change in temperature

i - the van't Hoff factor

Kt - The molal freezing point constant (cryoscopic constant)

m –Molality

At the lower freezing point, the vapor pressure of the liquid is

equal to the vapor pressure of the corresponding solid, and the
chemical potentials of the two phases are equal as well. The
equality of chemical potentials permits the evaluation of the
2
RM T f
cryoscopic constant as Kf = where ΔHfus is the solvent
∆ H fus
molar enthalpy of fusion.

Osmotic Pressure
Osmotic Preaaure is the difference in
pressure between the solution and the pure liquid solvent
when the two are in equilibrium across a semipermeable
membrane, which allows the passage of solvent molecules but
not of solute particles. If the two phases are at the same initial
pressure, there is a net transfer of solvent across the
membrane into the solution known as osmosis. The process
stops and equilibrium is attained when the pressure difference
equals the osmotic pressure.

The osmotic pressure is then proportional to the molar

concentration c, since,
nRTi
π= =cRTi
V

π – Osmotic pressure

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V -volumr

i – Van Hoff’s factor

The osmotic pressure is proportional to the

concentration of solute particles ci and is therefore a
colligative property.

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