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Beckmann Method for Freezing Point Depression

Beckmann and equilibrium methods can measure freezing point depression. The Beckmann method uses a freezing tube apparatus that contains the pure solvent. Its freezing point is measured, then the solute is added and the solution's freezing point is remeasured. The difference is the freezing point depression. The equilibrium method explains that at equilibrium, the chemical potential of the water in the solid and liquid phases must be equal. Adding solute dilutes the solvent, lowering the vapor pressure based on Raoult's law. This requires a lower temperature for the vapor pressures of the liquid and solid forms to be equal, causing freezing point depression.

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229 views3 pages

Beckmann Method for Freezing Point Depression

Beckmann and equilibrium methods can measure freezing point depression. The Beckmann method uses a freezing tube apparatus that contains the pure solvent. Its freezing point is measured, then the solute is added and the solution's freezing point is remeasured. The difference is the freezing point depression. The equilibrium method explains that at equilibrium, the chemical potential of the water in the solid and liquid phases must be equal. Adding solute dilutes the solvent, lowering the vapor pressure based on Raoult's law. This requires a lower temperature for the vapor pressures of the liquid and solid forms to be equal, causing freezing point depression.

Uploaded by

M.Hamid
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© All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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M.

Hamid Mahboob
Roll No: 138
Pharm-D(1st Prof.)

Measurement of Freezing Point Depression

There are two methods to measure depression in freezing point:

Beckmann Method
Equilibrium Method

Beckmann Method

Apparatus:
A simple Beckmann apparatus is shown in Fig. It consists of a freezing tube (a) with a side
arm (c) through which a known amount of a solute can be introduced. A stopper carrying a
Beckmann thermometer (b) and a stirrer (d) is fitted in to the freezing tube. To prevent rapid
cooling of the contents of the freezing tube, A, a guard tube (e) surrounds the tube so that
there is an air space between a and e. This assembly, as a whole, is placed in a wide vessel V
which contains a freezing mixture (f) maintaining a low temperature around 5C below the
freezing point of the pure solvent.
Procedure:
A known weight of the pure solvent is placed in the tube (a). It is cooled with gentle and
continuous stirring. As a result of super cooling, the temperature of the solvent will fall by about
0.5 deg C below its freezing point. Vigorous stirring is then set in when solid starts separating
and the temperature rises to the exact freezing point. This temperature remains constant, for
some time, until all the liquid solvent gets solidified and is noted as To.

 The tube (a) is taken out, warmed to melt the solid and a known weight of the solute is added
through the side arm (c). When the solute is dissolved in to the solvent forming a solution, the
tube (a) is put back in to the original position and the freezing point of the solution (T) is
redetermined in the same manner as before. The difference between the two readings gives the
freezing point depression (∆Tf).
Depression in freezing point ∆Tf = To-T. From this value, the molecular mass of the non-volatile
solute can be determined using the expression and known Kf value.

Beckmann Equation:

Equilibrium Method
Introduction:
Freezing point depression follows the colligative laws of thermodynamics at low
concentrations added to water. At the same time, the boiling point generally will be
increased. The freezing point depression can be readily explained from the theory of
phase equilibria in thermodynamics.

Explanation:
In equilibrium, the chemical potential must be equal in coexisting phases. The assumption is
that the solid phase must consist of one component, water, whereas the liquid phase will be a
mixture of water and salt. So the chemical potential for water in the solid phase μs is the
chemical potential of the pure substance. However, in the liquid phase, the water is diluted with
the salt. Therefore, the chemical potential of the water in liquid state must be corrected. x refers
to the mole fraction of the solute, that is, salt or an organic substance. The equation is valid for
small amounts of salt or additives in general:

Equation:

Freezing Point Depression in terms of Vapour Pressure:


The freezing point depression can also be explained in terms of vapor pressure. Adding solute
to a solvent will essentially dilute the solvent molecules, and according to Raoult’s law, this
leads to a decrease in vapor pressure. Considering the fact that the vapor pressure of the solid
and liquid forms must be the same at freezing point, because otherwise the system would not
be at equilibrium, the lowering of the vapor pressure leads to the lowering of the temperature at
which the vapor pressures of the liquid and frozen forms of the solution will be equal.

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