Methods
Methods
Methods
Hamid Mahboob
Roll No: 138
Pharm-D(1st Prof.)
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 5C 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: