For the determination of vapour pressures of low volatile compounds, conventional Knudsen
techniques (see Section 2.3.1), as well as conventional torsion-effusion techniques (see
Section 2.3.2) are used, all of which have their own merits. The combination of two of these
techniques in one set-up offers the opportunity of obtaining supplemental information, which
can be employed, for example, in studying the mutual consistency of the methods. Moreover,
the extra information can be used for the calculation of additional quantifies such as molar
mass or composition of the vapour phase [39-40].
The method of weighing effusion is based on Equation (2.1) formulated by Knudsen:
p- Cdm/dt, (2.4)
in which dm/dt represents the mass loss per unit time from an effusion cell. The constant
C among others contains the orifice area, molar mass, and the temperature of the effusing
species. In the torsion-effusion experiment with the effusion cell, the vapour pressure is
directly proportional to the torque, and is obtained by measurements of the electric compensation
current I according to Equation (2.3) and a value of C', which contains apparatus
constants only. A set-up in which torsion-effusion is combined with weighing effusion
is described in [40].
The advantage of the combined torsion method is that a direct measure of the vapour pressure
occurs with the mass loss of the Knudsen method, whereas with the torsion method the
molar mass is additionally included. Decomposition, dissociation or association of the sample
molecules would be immediately noticed because then the ratio Pm~ss loss/Ptorsion appears significantly
different from unity (it is unity for a pure substance). A disadvantage of this method
lies in the temperature measurement, which is performed in the measuring cell, but afar from
the sample. When the effusion flow rate varies, temperature fluctuations are usually ill defined.