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2. colligative properties 3

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25 views

2. colligative properties 3

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arnob7514
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ELEVATION OF BOILING POINT

When a liquid is heated, its vapor pressure rises and when it equals the atmospheric pressure, the liquid boils.
The addition of a non volatile solute lowers the vapor pressure and consequently elevates the boiling point as the solution has to
be heated to a higher temperature to make its vapor pressure become equal to atmospheric pressure.
If Tb is the boiling point of the solvent and T is the boiling point of the solution, the difference in the boiling points (ΔT) is
called the elevation of boiling point.
T – Tb = ΔT
The vapor pressure curves of the pure solvent, and solutions (1) and (2) with different concentrations of solute are shown in Fig

1
Relation between Elevation of Boiling Point and Lowering of Vapor-pressure

For dilute solutions, the curves BD and CE are parallel and straight lines approximately.
Therefore for similar triangles ACE and ABD, we have

where p – p1 and p – p2 are lowering of vapor pressure for


solution 1 and solution 2 respectively.
Hence the elevation of boiling point is directly proportional
to the lowering of vapor pressure.

or, ΔT ∝ p – ps

Relative lowering of vapor pressure

2
Determination of Molecular Mass from Elevation of Boiling Point

Since p is constant for the same solvent at a fixed


temperature, from the equation: ΔT ∝ p – ps we can write
If w/m = 1, W = 1, Kb = ΔT. Thus,
Molal elevation constant may be defined as the boiling-
But from Raoult’s Law for dilute solutions, point elevation produced when 1 mole of solute is
dissolved in one kg (1000 g) of the solvent.
If the mass of the solvent (W) is given in grams, it has to be
converted into kilograms then,
Since M (mol mass of solvent) is constant,

Therefore,

°C kg−solvent
The unit of Kb =
mol−solute
where Kb is a constant called Boiling point constant or
Ebulioscopic constant of molal elevation constant.
3
 The boiling point of a solution containing 0.20 g of a substance X in 20.00g of ether is 0.17 K
higher than that of pure ether. Calculate the molecular mass of X. Boiling point constant of
ether per 1 Kg is 2.16 K.

 During a determination, 22 g of benzene was used as solvent. The readings on the differential
thermometer before and after adding 0.586 g of naphthalene (mol mass = 128), were 1.262
and 1.799 respectively. In a separate experiment, using the same amount of benzene but this
time adding 0.627 g of an organic compound X, the temperature readings were 1.269 and
1.963. Calculate the molecular mass of X.

4
MEASUREMENT OF BOILING–POINT ELEVATION

(i) An inner tube with a hole in its side and graduated in ml;
(ii) A boiling flask which sends solvent vapor in to the
graduated tube through a ‘rosehead’ (a bulb with several
holes)’
(iii) An outer tube which receives hot solvent vapour issuing
from the side-hole of the inner tube;
(iv) A thermometer reading to 0.01 K, dipping in solvent or
solution in the inner tube.

5
FREEZING–POINT DEPRESSION
Relation between Depression of Freezing-point and Lowering of Vapour-pressure

For dilute solutions FD and CE are approximately parallel


straight lines and BC is also a straight line. Since the triangles
BDF and BEC are similar,

where p1 and p2 are vapour pressure of solution 1 and solution 2


respectively. Hence depression of freezing point is directly
proportional to the lowering of vapour pressure.

Tf – T1 = Δ T
6
Determination of Molecular Weight from Depression of Freezing point

Since p is constant for the same solvent at a fixed


temperature, from equation ΔT ∝ p – ps we can
where Kf is a constant called Freezing-point constant or Cryoscopic
write
constant or Molal depression constant. If w/m = 1 and W = 1, Kf = ΔT.
Thus,
Molal depression constant may be defined as the freezing-point
from Raoult’s Law for dilute solutions depression produced when 1 mole of solute is dissolved in one kg
(1000 g) of the solvent.
If the mass of solvent (W) is given in grams, it has to be converted into
kilograms. Thus

Since M (mol wt) of solvent is constant

we can write

Where, m = molecular mass of solute ;


Kf = molal depression constant ;
w = mass of solute ;
ΔT = depression of freezing point ;
W = mass of solvent 7
 A solution of 0.124 g of a substance, X, in 25.0 L of ethanoic acid (acetic acid)
has a freezing point 0.324°C below that of the pure acid 16.6°C. Calculate the
molecular mass (relative molecular mass) of X, given that the specific latent heat
of fusion of ethanoic acid is 180.75 J g–1.

 The aqueous solutions contain same amount (in gram) of glucose and sugar
separately in the same amount of water. Which of the two solutions will have
lower freezing point? Explain your answer.

8
Measurement of Freezing–Point Depression (Beckmann’s Method)

(i) A freezing tube with a side-arm to contain the


solvent or solution, while the solute can be introduced
through the side-arm;
(ii) An outer larger tube into which is fixed the freezing
tube, the space in between providing an air jacket
which ensures a slower and more uniform rate of
cooling;
(iii) A large jar containing a freezing mixture e.g., ice
and salt, and having a stirrer.

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