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To determine the relative molecular mass of unknown compound by endpoint cryoscopy.


The freezing point of a dilute solution is lower than that of the pure solvent if the solid which
freezes out of solution is pure solvent and not a solid solution. Under these conditions the
lowering of the freezing point is proportional to the mole fraction of the solute in solution. If
the solution is very dilute, this relationship can be expressed as

Δ T = k [W (solute) / M (solute)] … (1)

where Δ T = depression of freezing point

k = cryoscopic constant (freezing point depression constant)

W (solute) = mass of solute per 1000 g of solvent

M (solute) = molar mass of solute

In this experiment, the freezing point is determined by the method called end point
cryoscopy. A solution of known concentration is partly frozen and then allowed to melt
slowly whilst being stirred so as to maintain thermal equilibrium. The temperature rises
slowly until all solid has melted as heat of fusion is taken up to convert solid to liquid. The
plot generally shows two linear branches from the intersection of which the freezing point of
the solution can be obtained.

Apparatus and Materials

Boiling tube, salt / ice / water bath, stopwatch, thermometer (-20 ºC to + 30 ºC, graduated in
1 / 10 ºC), stirrer, 20 cm3 and 2 cm3 pipettes (both fitted with suction bulb), benzene,
naphthalene, unknown liquid.

Experimental Procedure

Benzene is used as the solvent in this experiment because it is readily available, possesses a
convenient freezing point, and has a relatively large cryoscopic constant.

a) Determination of freezing point of pure solvent. Pipette exactly 20 cm3 of benzene into a
pyrex boiling tube and cool it in a salt / ice / water bath until about one half of it has frozen.
Then clamp it vertically, insert a (1 / 10 ºC) thermometer, stir gently and note the temperature
at 1 / 2 minute intervals until all the solid has melted and then for a further 3 minutes. The
melting portion of the (temperature versus time) curve should be flat for a pure substance.

b) Determination of cryoscopic constant of benzene. The freezing point of pure benzene (T0)
is obtained in (a). Add an accurately known mass of naphthalene (ca. 1.0 g) to the 20 cm3 of
benzene used in (a) and determine the melting curve for the solution as described in (a).

c) Determination of relative molecular mass of unknown compound. Pipette exactly 2 cm3 of

the unknown liquid into a boiling tube containing exactly 20 cm3 of benzene. Determine the
freezing point of this solution as described in (a) ( = Tu).

Results and Calculations

The result from (a) provides the freezing point of pure benzene (T0). The result from (b)
provides the freezing point of a solution of naphthalene of known concentration in benzene

Knowing ΔT (T = T0 – T) and W (naphthalene) for this solution, it is possible to calculate k

for benzene from equation (1). M (naphthalene) = 128.3 g; density (benzene) = 0.879 g cm-3
at 20 ºC.

The freezing depression of the unknown solution (T0 – Tu) is known from (c). k and W
(unknown solute) are also both known, so that it is possible to determine the molar mass of
the unknown from equation (1). (Density of unknown liquid = 0.861 g cm-3 at 20 ºC).