Interpreting chemical kinetics from complex reaction-advection-diffusion systems: Modeling of flow reactors and related experiments

The present discourse is directed toward the community that wishes to generate or use flow reactor data from complex chemical reactions as kinetic model development and validation targets. Various methods for comparing experimental data and computational predictions are in evidence in the literature, along with limited insights into uncertainties associated with each approach. Plug flow is most often assumed in such works as a simple, chemically insightful physical reactor model; however, only brief qualitative justifications for such an interpretation are typically offered. Modern tools permit the researcher to quantitatively confirm the validity of this assumption. In a single complex reaction system, chemical time scales can change dramatically with extent of reaction of the original reactants and with transitions across boundaries separating low temperature, intermediate temperature, and chain branched (high temperature) kinetic regimes. Such transitions can violate the underlying assumptions for plug flow interpretation. Further, uncertainties in reaction initialization may confound interpretation of experiments for which the plug flow assumption may be appropriate. Finally, various methods of acquiring experimental data can also significantly influence experimental interpretations. The following discussions provide important background for those interested in critically approaching the relatively vast literature on the application of flow reactors for generating kinetic validation data. The less frequently discussed influences of reactor simulation assumptions on modeling predictions are addressed through examples for which the kinetic behavior of specific reactant combinations may cause experimental observations to depart locally from plug flow behavior. (C) 2014 Elsevier Ltd. All rights reserved.