Development of Theoretical Methods for Predicting Solvent Effects on Reaction Rates in Supercritical Water Oxidation Processes
Abstract
The design of efficient supercritical water oxidation reactors for the destruction of chemical warfare agents will be facilitated by computational fluid dynamics modeling of these systems. To assist such modeling efforts, the aim of this project is to develop computational methods for predicting how reaction rate constants will vary with thermodynamic condition in supercritical water (SCW). Towards this end, two reactions were examined in SCW: the anisole hydrolysis reaction and the hydrogen peroxide dissociation reaction. For the anisole reaction, the nature of the microscopic viscosity on this reaction was examined as a function of thermodynamic condition and reaction path progress. An interesting interplay of sensitivity to these variables was observed as were strong local density effects in the compressible regime. However, reaction studies indicate that, in spite of the magnitude of the observed compression-induced anomalies, their effect on the reaction rate is expected to be less than a few percent, such that these effects can likely be neglected in reactor modeling. For the hydrogen peroxide dissociation, high-level quantum chemistry calculations suggest that earlier solvation studies on this reaction need to be reconsidered in light of more accurate charge distributions. As well, solvation studies suggest not only that solvation effects may be larger than anticipated for this reaction, especially at very low water densities, but also that polarization may play a critical role, such that standard fixed charge studies will be inaccurate. A list of related journal articles and symposium papers is included.
Document Details
- Document Type
- Technical Report
- Publication Date
- Jun 12, 2003
- Accession Number
- ADA429257
Entities
People
- Susan C. Tucker
Organizations
- University of California