Calculation of the Vapour Pressure of Organic Molecules by Means of a Group-Additivity Method and Their Resultant Gibbs Free Energy and Entropy of Vaporization at 298.15 K

The calculation of the vapour pressure of organic molecules at 298.15 K is presented using a commonly applicable computer algorithm based on the group-additivity method. The basic principle of this method rests on the complete breakdown of the molecules into their constituting atoms, further characterized by their immediate neighbour atoms. The group contributions are calculated by means of a fast Gauss-Seidel fitting algorithm using the experimental data of 2036 molecules from literature. A ten-fold cross-validation procedure has been carried out to test the applicability of this method, which confirmed excellent quality for the prediction of the vapour pressure, expressed in log(pa), with a cross-validated correlation coefficient Q(2) of 0.9938 and a standard deviation sigma of 0.26. Based on these data, the molecules' standard Gibbs free energy Delta G degrees(vap) has been calculated. Furthermore, using their enthalpies of vaporization, predicted by an analogous group-additivity approach published earlier, the standard entropy of vaporization Delta S degrees(vap) has been determined and compared with experimental data of 1129 molecules, exhibiting excellent conformance with a correlation coefficient R-2 of 0.9598, a standard error sigma of 8.14 J/mol/K and a medium absolute deviation of 4.68%.

Automated summary

The study presented a calculation of the vapor pressure of organic molecules at 298.15 K using a group-additivity method, with excellent quality for prediction.