Chemistry

Topic
Explain Raoult’s law for an Ideal solution.
Explain Colligative properties with one method
1. Lowering of vapour pressure
2. Elevation in boiling point.
3. Depression in freezing point

Submitted to : Sadia Bashir

Submitted by : Muzammil Shabeer
Roll no : Bsf-2000554

Introduction

François-Marie Raoult, French chemist who formulated a law on solutions (called

Raoult’s law) that made it possible to determine the molecular weights of dissolved substances
.

Statement :
Raoult’s law states that a solvent’s partial vapour pressure in a solution (or
mixture) is equal or identical to the vapour pressure of the pure solvent multiplied by its mole
fraction in the solution.
Mathematical Form:
Mathematically, Raoult’s law equation is written as;
Solution = Χsolvent . Psolvent
Solution = vapour pressure of the solution
Χsolvent = mole fraction of the solvent
Psolvent = vapour pressure of the pure solvent

Volatile liquid:-
Consider a solution of volatile liquids A and B
in a container. Because A and B are both volatile, there would be
both particles of A and B in the vapour phase.
Hence, the vapour particles of both A and B exert partial
pressure which contributes to the total pressure above the
solution.

Further, Raoult’s law states that at equilibrium,PA = P°A xA ,PB = P°B xBWhere PA is the
partial pressure of AP°A is the vapour pressure of pure A at the corresponding temperature. XA
is the mole fraction which is in the liquid phaseSimilarly,PB , P°B xBHence.

Non- Volatile:-
 If a non-volatile solute B (zero vapor pressure, does not evaporate) is dissolved
into a solvent A to form an ideal solution, the vapor pressure of the solution will be lower than
that of the solvent. In an ideal solution of a nonvolatile solute, the decrease in vapor pressure is
directly proportional to the mole fraction of solute:

Why Raoult's Law works:-

If you look review the concepts of colligative properties, you will find that adding a
solute lowers vapor pressure because the additional solute particles will fill the gaps between the
solvent particles and take up space. This means less of the solvent will be on the surface and less
will be able to break free to enter the gas phase, resulting in a lower vapor pressure. There are
two way of explaining why Raoult's Law works .
1. a simple visual way
2. a more sophisticated way based on entropy. Below is the simple approach.

Remember that saturated vapor pressure is what you get when a liquid is in a sealed container.
An equilibrium is set up where the number of particles breaking away from the surface is exactly
the same as the number sticking on to the surface again.

Importance of Raoult’s law:-

Assume that we have a
closed container filled with a volatile liquid A. After some
time, due to evaporation, vapour particles of A will start to
form. Then as time passes, the vapour particles of A will
be in dynamic equilibrium with the liquid particles (on the
surface). The pressure exerted by the vapour particles of A
at any particular temperature is called the vapour
pressure of A at that temperature.

Vapour pressure is exhibited by all solids and liquids and depends only on the type of liquid and
temperature.

Now imagine we are adding another liquid B (solute) to

this container. This will result in B particles occupying the
space between A particles on the surface of the solution.
For any given liquid there are a fraction of molecules on the surface which will have sufficient
energy to escape to the vapour phase.

Since now we have a lesser number of A particles on the surface, the number of vapour particles
of A in the vapour phase will be lesser. This will result in lower vapour pressure of A.

Now if we assume that B is volatile as well, we will have lesser number of B particles in the
vapour phase as compared to pure liquid B.

This new pressure (partial pressure) of each (A and B) is given by Raoult’s law and depends on
the concentration of each component in the liquid phase.

P A∝ XA ,PB ∝XB=

XA PAo = XB PBo
From Raoult’s law it is evident that as the mole fraction of a component reduces, its partial
pressure also reduces in the vapour phase.

The graphs below show pressure is the mole fraction for A and B.

Combining both the graphs.

In the above diagram, we have also added the graph for the total vapour pressure of solution i.e.
PA + PB.

As far as the application of the law goes, it is also useful in calculating the molecular mass of an
unknown solute.

Relation of Raoult's with Ideal solution:-

 Raoult's Law only works for ideal solutions. "An ideal solution shows thermodynamic
mixing characteristics identical to those of ideal gas mixtures ideal solutions have
intermolecular interactions equal to those of the pure components." Like many other
concepts explored in Chemistry, Raoult's Law only applies under ideal conditions in an

ideal solution fraction of the component in a solution at a given temperature.

 The enthalpy of mixing is zero, i.e. ΔHmix = 0. It means that no heat is absorbed or
released.

 The volume of mixing is zero, ΔVmix = 0. It means that the volume of the solution is equal
to the sum of the volume of components.

Limitations on Raoult's Law:-

In practice, there's no such thing as an ideal solution! However, features of one include:

 Ideal solutions satisfy Raoult's Law.

 it is far too concentrated, but was drawn so concentrated to emphasized the point.
 In an ideal solution, it takes exactly the same amount of energy for a solvent molecule to
break away from the surface of the solution as it did in the pure solvent.
  The forces of attraction between solvent and solute are exactly the same as between the
original solvent molecules - not a very likely event!

Colligative properties:-
A colligative property is a property of a solution that is dependent on the ratio between the total
number of solute particles (in the solution) to the total number of solvent particles. Colligative
properties are not dependent on the chemical nature of the solution’s components. Thus,
colligative properties can be linked to several quantities that express the concentration of a
solution, such as molarity, normality, and molality. The four colligative properties that can be
exhibited by a solution are:

 Boiling point elevation

 Freezing point depression
 Relative lowering of vapour pressure
 Osmotic pressure
The word “colligative” has been adapted or taken from the Latin word “colligatus” which
translates to “bound together”. In the context of defining a solution, colligative properties help us
understand how the properties of the solution are linked to the concentration of solute in the
solution.

1. Lowering of Vapour Pressure

In a pure solvent, the entire surface is occupied by the
molecules of the solvent. If a non- volatile solute is added to the solvent, the surface now has
both solute and solvent molecules; thereby fraction of surface covered by solvent molecules gets
reduced. Since the vapour pressure of the solution is solely due to solvent alone, at the same
temperature the vapour pressure of the solution is found to be lower than that of the pure solvent.
If P0 is the vapour pressure of pure solvent and Ps is the vapour pressure of the solution. The
difference Po – Ps is termed as lowering in vapour pressure. The ratio Po – Ps / Po is known as
the relative lowering of vapour pressure.
Raoult, in 1886, established a relation between relative lowering in vapour pressure and mole
fraction. The relationship is known as Raoult’s law. It states that the relative lowering in vapour
pressure of a dilute solution is equal to the mole fraction of the solute present in the solution
If n moles of solute is dissolved in N moles of the solvent, then according to Raoult’s law.
Po – Ps / Po = n / n + N
Methods To measure Vapour pressure

Measurement of Lowering of Vapour Pressure by Ostwald and Walker Method:-

A number of other devices have been developed for measurement of the difference of vapor
pressure. All these are known as static methods to differentiate them from the dynamic method
due to Ostwald and Walker which is described below. In this method, the relative lowering of
vapor pressure can be determined directly. The measurement of the individual vapor pressures of
a solution and solvent is thus eliminated.

Method:-

 stream of dry air is bubbled successively through the solution.

 the pure solvent

 a reagent which can absorb the vapor of the solvent

 As the solvent is usually water the reagent is generally anhydrous Calcium Chloride

Procedure

 The apparatus used is shown in the figure. It consists of two sets of bulbs. The first set of
three bulbs is filled with the solution to half of their competence and second set of
another three bulbs is filled with the untainted solvent.

 Each set is separately weighed accurately. Both sets are linked to each other and then
with the accurately weighed set of guard tubes filled with anhydrous calcium chloride.
 The bulbs of the solution and pure solvent are reserved in a thermostat maintained at a
stable temperature.

 In this method, the solution and the solvent are taken in a series of gas washing bottles
and a slow stream of dry air or nitrogen is bubbled through the solution and the solvent.
The first three bulbs surround a weighed amount of the solution under assessment and the
next three bulbs surround a weighed amount of the pure solvent

 . A weighed amount of anhydrous calcium chloride is taken in the set of U-tubes at the
end. The stream of gas coming out through D is saturated with the solvent vapor which is
absorbed in a series of absorption tubes containing a suitable absorbing agent.

 The dry gas after passage through the solution becomes saturated with the solvent vapor
from the pure solvent because the vapor pressure of the solvent is higher than that of the
solution. The gas on passage through the solvent carries with it more vapor from it.

 After a sufficient flow of the gas, the absorption tubes and the two series of washing
bottles are separately weighted. The increase in the mass of the absorption tube is
proportional to the vapor pressure of the solvent and the loss in mass of the bottles
containing solution is proportional to the vapor pressure of the solution, which loss in
mass of the bottles, B, is proportioned to the lowering of vapor pressure.

2. Elevation in Boiling Point:-

The boiling point of a liquid is the temperature at which the vapour pressure is equal to
atmospheric pressure. We know that on the addition of a non-volatile liquid to a pure solvent, the
vapour pressure of a solution decrease. Therefore to make vapour pressure equal to atmospheric
pressure we have to increase the temperature of the solution. The difference in the boiling point
of the solution and the boiling point of the pure solvent is termed as elevation in boiling point..
If T0b is the boiling point of the pure solvent and Tb is the boiling point of the solution then
elevation in boiling point is given as
∆Tb =T0b-Tb
Experimental results show that there is a relation between elevation in boiling point and molality
‘m’ of the solute present in solution
∆Tb ∝ m
∆Tb = kb m
Where,
kb = molal elevation constant
Substituting the value of ‘m’ in the above relation we get
∆Tb = 1000 x kb x m2 / M2 x m1
Where,
m2 = mass of solvent in g
M1 = mass of solvent in kg
M2 = molar mass of solute.

Method to measure boiling point

Land Berger’s Method:-
A graduated inner tube with a hole in its side B. A boiling flask which sends the solvent vapors
into the inner tube through a nose head C. An outer tube which receives solvent vapors coming
out from the side hole of the inner tube D.

1. The solvent of boiling point, T0, is boiled in a separate flask and used to boil
the solution.
2. Excess vapor escapes through the hole E.

3. The boiling point of the solution T 10C is obtained

from the thermometer.
4. The final volume of the liquid in the graduated
tube is read off and from the density of the
solvent the mass (ms g) of the solvent into which
a solute of mass m2 is dissolved is calculated.
Then the boiling point constant Kb is given by

3. Depressions in freezing point

The freezing point of a substance is defined as the

temperature at which the vapour pressure of its liquid is equal to the vapour of the corresponding
solid. According to Raoult’s law when a non-volatile solid is added to the solvent its vapour
pressure decreases and now it would become equal to that of solid solvent at a lower
temperature. The difference between the freezing point of the pure solvent and its solution is
called depression in freezing point.
If T0f is the boiling point of the pure solvent and Tf is the boiling point of the solution then
depression in freezing point is given as
∆Tf =T0f-Tf
Just like elevation in boiling point, depression in freezing point is also directly related to molality
‘m’.
∆Tf = 1000 x kf x m2 / M2 x m1
Where,
k f = molal depression constant
m2 = mass of solvent in g
M1 = mass of solvent in kg
M2 = molar mass of solute

Method to measure depression in freezing point:

Rast Method:-
 The Rast method, one of the older techniques for finding the molecular mass of an
unknown, measures the freezing point depression of solution in camphor.
 Camphor is used because its freezing point is very sensitive to added solution solute (It
has highest `K_(f))`.
 A solution of `2.342 g` of an unknown substancein `49.88 g` of camphor freezes at `441.2
K`. If `K_(f)` for camphor is `40.0 Kg mol^(-1)`
 , calculate the molecular mass of the unknown. Strategy: Find the molality of the solution
from the freezing point of the pure camphor, the freezing point of the solution and the
value of `K_(f)` by using the relationship `DeltaT_(f)=K_(f)m`.
 From the molality, find the no. of moles of solute in given mass of solvent. Finally find
the molar mass (Melting point of pure camphar is 453.0 K)

References
https://byjus.com/jee/colligative-properties/
https://openstax.org/books/chemistry-2e/pages/11-4-colligative-properties