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TOPIC: COLLIGATIVE PROPERTIES

Sub: Physical Chemistry
BSc Part I

By

Miss Ipsha shruti

Department of Chemistry
A.S. College, Bikramganj
 Introduction
Raoult’s law:

In 1986, a French Chemist named Francois Marte Raoult proposed a quantitative

relation between partial pressure and mole fraction of volatile liquids. The law states
that partial vapour pressure of a solvent in a solution is equal to the vapour pressure
of the pure solvent multiplied by its mole fraction in the solution.
Mathematically, Raoult’s law equation is written as;
Psolution = ΧsolventP0solvent
Where,
Psolution = vapour pressure of the solution
Χsolvent = mole fraction of the solvent
P0solvent = vapour pressure of the pure solvent
Ideal and Non-ideal solutions
On the basis of Raoult’s Law, liquid-liquid solutions are classified into two types of solutions,
they are:
• Ideal Solutions
• Non-ideal Solutions
The solutions which obey Raoult’s law at all compositions of solute in solvent at all temperature
are called ideal solutions.

An ideal solution should have following characteristics

• It should obey Raoult’s law
• Δ Hmixing = 0, i.e. no heat should be absorbed or evolved during mixing
• ΔVmixing = 0, i.e. no expansion or contraction on mixing
• Two liquids A and B form an ideal solution when A –A and B–B molecular
attractions will be same and hence A–B molecular atrraction will be almost same
as A–A and B–B molecular attraction.
PA = ΧAP0A
Where PA is the partial pressure of A.
P0A is vapour pressure of pure A at that temperature.
ΧA is mole fraction of A in the liquid phase.
Similarily, PB= ΧBP0B
Examples of Ideal solutions:
 Ethyl chloride and ethyl bromide
 n–hexane and n–heptane
 CCl4 and SiCl4
• The solution which deviate from ideal behavior are called non ideal solution or
real solutions and they do not obey Raoult’s law over entire range of composition.

• It has been found that on increasing dilution, a non ideal solution tend to be ideal.
• For non ideal solutions,

• i.e, they do not obey Raoult’s law

• Case: I

Such a solution shows positive deviation from Raoult’s Law

e.g. cyclohexane and ethanol.

(In ethanol the molecules are held together due to hydrogen bonding, when cyclohexane is
added to ethanol the molecules of cyclohexane tend to occupy the space between ethanol
molecules due to which some hydrogen bonds break due to which inter molecular attraction
between cyclohexane and ethanol is reduced and hence show higher vapour pressure.)
• Case: II

Solutions of above type show negative deviation from Raoult’s law and their
observed boiling point is found to be higher than the calculated value

eg. When acetone and chloroform are mixed together a hydrogen bond is formed between
them which increases inter molecular attraction between them and hence decreases the vapour
pressure.
 Colligative properties
The dilute solutions show more or less ideal behavior and obey Raoult’s law. The
properties of dilute solutions which depend only on number particles of solute
present in the solution and not on their identity are called colligative properties.
Here the solute is assumed to be non-volatile.
The various colligative properties are:
 Lowering of vapour pressure
 Elevation of boiling point
 Depression of freezing point
 Osmotic pressure
 Lowering of vapour pressure
• when a non-volatile solute is dissolved in a liquid, the vapour pressure of the
solution becomes lower than the vapour pressure of the pure solvent.
• Let us consider n moles of a non-volatile solute is dissolved in N moles of a
volatile solvent. Then mole fraction of the solvent, X 1 = N/(n+N) and mole
fraction of the solute, X2 = n /(N +n).
• According to Raoult's law, the vapour pressure of a solvent (P1) in an ideal
solution is given by the expression;
P1 = X1 P10......................... (1)
where P10 is the vapour pressure of the pure solvent. Since X1 + X 2 = 1, Eq. 1 may
be written as
Equation 3 can be stated as
“The relative lowering of vapour pressure of a
solution containing a non-volatile solute is equal
to the mole fraction of the solute present in the
solution.'
• Since mole fraction of the solute, X2 is given by n/(N+n), Equation (3) may be
expressed as

• From Equation (4) that the lowering of vapour pressure of a solution depends
upon the number of moles (and hence on the number of molecules) of the solute
and not upon the nature of the solute dissolved in a given amount of the solvent.
Hence, lowering of vapour pressure is a colligative property.
 Determination of Molar Masses from Lowering of Vapour Pressure
• It is possible to calculate molar masses of non-volatile non-electrolytic solutes by
measuring vapour pressures of their dilute solutions.
• Suppose, a given mass, w gram, of a solute of molar mass m, dissolved in W
gram of solvent of molar mass M, lowers the vapour pressure from P10 to P1.
Then, by equation (4)

Since in dilute solutions, n is very small as compared to N, Equation (5) may

be put in the approximate form as
Elevation of boiling point
• The boiling point of a liquid is the temperature at which its vapour pressure
becomes equal atmospheric pressure. Since

• Addition of a non-volatile solute lowers the vapour pressure of the solvent

• The vapour pressure of a solution is always lower than that of the pure solvent,
and hence it must be heated to a higher temperature to make its vapour pressure
equal to atmospheric pressure.

• Thus the solution boils at a higher temperature than the pure solvent. If Tb0 is the
boiling point of the solvent and Tb is the boiling point of the solution, the
difference in boiling points (ΔTb) is called the elevation of boiling point
 ΔTb= Tb-Tb0
Tbα m

ΔTb = Kb x m
Kb : molal elevation constant or
Ebullioscopic constant

m : molality of the solution

Boiling point elevation in a dilute solution is directly proportional to the number

of moles of the solute dissolved in a given amount of the solvent and is quite
independent of the nature of the solute. Hence, boiling point elevation is a
colligative property
• Molal boiling point elevation constant or ebullioscopic constant of the solvent, is
defined as the elevation in boiling point which may theoretically be produced by
dissolving one mole of any solute in 1000 g of the solvent.

where m1 = molecular weight of solute and w and W are weights of solute

and solvent
DEPRESSION OF FREEZING POINT BY A NON-VOLATILE SOLUTE
• Freezing point is the temperature at which solid and liquid states of a substance
have the same vapour pressure.
• It is observed that the freezing point of the solution (Tf) containing non volatile
solute is always less than the freezing point of the pure solvent (T ). Thus, T 0 - T
0
f f f
= ΔTf

• It can be seen that Tf α m or, ΔTf = Kf x m

Kf : molal freezing point depression constant

of the solvent or cryoscopic constant
m : molality of the solution
• Molal freezing point depression constant of the solvent or cryoscopic constant, is
defined as the depression in freezing point which may theoretically be produced
by dissolving 1 mole of any solute in 1000g of the solvent.

where m1 = molecular weight of solute and w and W are weights of solute and
solvent
• Thus, freezing point depression of a dilute solution is directly proportional to the
number of moles of the solute dissolved in a given amount of the solvent and is
independent of the nature of solute.
 OSMOSIS AND OSMOTIC PRESSURE
The phenomenon of the passage of pure solvent from a region of lower
concentration (of the solution) to a region of its higher concentration through a
semi-permeable membrane is called osmosis.

The difference in the pressure between the solution

And the solvent system is called osmotic pressure.
It is the excess pressure which must be applied to a
solution in order to prevent flow of solvent into the

solutionthrough the semi-permeable membrane.

• Van't Hoff equation for dilute solutions is
πV = nRT
where π = Osmotic pressure,
V= volume of solution,
n= no. of moles of solute that is dissolved,
R = Gas constant,
T= Absolute temperature

(Isotonic Solutions: A pair of solutions having same osomotic pressure is called isotonic solutions.)
Reverse Osmosis
When a solution is separated from pure water by a
semipermeable membrane, water moves towards
solution on account of osmosis. This process
continues till osmotic pressure becomes equal to
hydrostatic pressure or osmosis can be stopped by
applying external pressure equal to osmotic pressure
on solution. If external pressure greater than osmotic
pressure is applied, the flow of solvent molecules can
be made to proceed from solution towards pure
solvent, i.e., in reverse direction of the ordinary
osmosis. This type of osmosis is termed reverse
osmosis. Reverse osmosis is used for the desalination
of sea water for getting fresh drinking water.
Referred Books:

• P. Atkins and J. de Paula, Physical Chemistry, 9th Edition, W. H. Freeman, 2009

• K.L. Kapoor, A Textbook of Physical Chemistry, 2nd Edition, Macmillan, 2011

• G.W. Castellan, Physical Chemistry, 3rd Edition, Addison Wesley, 1983

• Puri, Sharma, Pathania, Principle of Physical chemistry, 44th edition, 2010

• I.N. Levine, Physical Chemistry, 6th Edition, McGraw-Hill, 2008.