A revised equation for estimating the vapour pressure of low-volatility substances from isothermal TG data

Previous investigators have used the Langmuir vaporisation relation to estimate the vapour pressures of low-volatility compounds from thermogravimetric data. However, this equation is strictly valid for evaporation into a vacuum only. For measurements conducted at finite pressures, molecular diffusion must be taken into account. A revised equation is proposed: dm(A)/dtproportional toM(A)P(A)D(AB)/T. It is also shown that the proportionality between vapour pressure and vaporisation rate is very general. It arises from the assumptions of ideal gas behaviour, Raoult's law and a negligible concentration of the sample compound far from the sample surface.