Proposal Number: CTS-0086700 Principal Investigator: Richard Masel Institution: University of Illinois
The objective of this proposal is to develop improved engineering approximations for chemical kinetics. The ability to estimate kinetic parameters is of importance to the chemical process industry for process design and optimization. More accurate correlations for reaction rate constants will be developed using a combination of ab initio quantum mechanics methods and experimental data. In previous efforts an improved correlation for estimating the activation energy of atom transfer reactions, requiring one adjustable parameter, was developed. In the current project previous efforts to calculate rates of the general hydrogen abstraction reaction will be extended. Reactions involving various free radicals including hydroxyl, alkyl, and chlorine will be examined. Reactants containing primary, secondary, and tertiary carbon-hydrogen bonds will also be studied to fit and test the applicability of the model. Ab initio calculations will be performed to determine the activation barriers and the intermolecular forces between reactants during reaction. These calculations will permit an estimate of the relative importance of each term in the predicted overall rate. This work may lead to better models for the prediction of kinetic data for use in chemical reaction process simulators.
