We have computed molecular descriptors for sizes, shapes, charge distributions, and dispersion interactions for 67 compounds using quantum chemical ab initio and density functional theory methods. For the same compounds, we have fitted the three perturbed-chain polar statistical associating fluid theory (PCP-SAFT) equation of state (EOS) parameters to experimental data and have performed a statistical analysis for relations between the descriptors and the EOS parameters. On this basis, an analysis of the physical significance of the parameters, the limits of the present descriptors, and the PCP-SAFT EOS has been performed. The result is a method that can be used to estimate the vapor pressure curve including the normal boiling point, the liquid volume, the enthalpy of vaporization, the critical data, mixture properties, and so on. When only two of the three parameters are predicted and one is adjusted to experimental normal boiling point data, excellent predictions of all investigated pure compound and mixture properties are obtained. We are convinced that the methodology presented in this work will lead to new EOS applications as well as improved EOS models whose predictive performance is likely to surpass that of most present quantum chemically based, quantitative structure-property relationship, and group contribution methods for a broad range of chemical substances.

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This kinetic analysis compares homogeneous and heterogeneous catalysts for the cyclization of 6-aminoha-1-yne. The reaction was studied as a model for the direct addition of amine N -H bonds to CC multiple bonds (hydroamination). Kinetic modeling showed that the metal-catalyzed hydroamination reaction is followed by a proton-catalyzed isomerization of the primary reaction product, 2-methylene-piperidine, to the thermodynamically more stable 2-methyl-l,2-dehydropiperidine.

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