The present research focuses on the extension of the automatic kinetic model generator Genesys to liquid-phase processes as opposed to the current gas-phase applications. An accurate estimation of the solvation free energy is important both for thermodynamic parameters, e.g. equilibrium coefficients, as well as for reaction rate coefficients. An empirical method has been developed in the past, the so-called Abrahams method1, which is a linear free energy relationship used in combination with Platts Fragments2, an approach similar to group additivity, and can be further extended to incorporate temperature dependence. In this work, these approaches have been implemented in Genesys, with readily available data which reproduce literature results. However, the underlying databases are insufficient to study real processes, and Genesys is now also able to automatically calculate solvation free energies using a combination of ab initio and semi-empirical calculations, c.f. Figure 1. The different levels of calculations, at different computational costs, are thus used to extend the Platts values databases. To verify the quality of the results, Genesys has been used to reproduce solvation free energies from the Minnesota solvation database.

Assessment for the inclusion of liquid-phase chemistry in automatic kinetic model generation

2019 Fall National Meeting

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.