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Automated model building and modeling of alcohol oxidation in high temperature water
Sadasivan D. Iyer,
Prasanna V. Joshi,
Michael T. Klein,
Sadasivan D. Iyer
Department of Chemical Engineering, University of Delaware, Newark, DE 19716
Search for more papers by this authorPrasanna V. Joshi
Department of Chemical Engineering, University of Delaware, Newark, DE 19716
Search for more papers by this authorMichael T. Klein
Department of Chemical Engineering, University of Delaware, Newark, DE 19716
Search for more papers by this authorSadasivan D. Iyer,
Prasanna V. Joshi,
Michael T. Klein,
Sadasivan D. Iyer
Department of Chemical Engineering, University of Delaware, Newark, DE 19716
Search for more papers by this authorPrasanna V. Joshi
Department of Chemical Engineering, University of Delaware, Newark, DE 19716
Search for more papers by this authorMichael T. Klein
Department of Chemical Engineering, University of Delaware, Newark, DE 19716
Search for more papers by this authorAbstract
Software for the computer generation of kinetic models was exploited to construct a mechanistic kinetic model for alcohol oxidation in high temperature (300 ≤T/°C≤380) water. The complexities of the oxidation mechanism were captured by a detailed mechanism consisting of eight reaction families. These included hydrogen abstraction by oxygen, hydrogen abstraction by radical, β-scission, non-terminating radical reactions, isomerizations, decomposition, molecular addition and termination steps. The mechanistic model was generated computationally, using the graph theory notions where the molecules and radicals are represented as atomic connectivity matrices and the reactions as matrix operators. The free-radical kinetics of C1-C4 alcohols exhibited features of both gas-phase combustion and liquid-phase oxidation chemistry. The imposition of Evans-Polanyi relationships for the associated rate constants provided a significant reduction in model parameters with little loss of predictive capability. Kinetic parameter vectors, one for each reaction family, obtained by optimizing the model predictions to pure-component ethanol data provided a very good fit to pure component kinetics of other alcohols, as well as mixture kinetics.
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