  Temporal analysis of products (TAP) reactors enable experiments that probe
numerous kinetic processes within a single set of experimental data through
variations in pulse intensity, delay, or temperature. Selecting additional TAP
experiments often involves arbitrary selection of reaction conditions or the
use of chemical intuition. To make experiment selection in TAP more robust, we
explore the efficacy of model-based design of experiments (MBDoE) for precision
in TAP reactor kinetic modeling. We successfully applied this approach to a
case study of synthetic oxidative propane dehydrogenation (OPDH) that involves
pulses of propane and oxygen. We found that experiments identified as optimal
through the MBDoE for precision generally reduce parameter uncertainties to a
higher degree than alternative experiments. The performance of MBDoE for model
divergence was also explored for OPDH, with the relevant active sites (catalyst
structure) being unknown. An experiment that maximized the divergence between
the three proposed mechanisms was identified and led to clear mechanism
discrimination. However, re-optimization of kinetic parameters eliminated the
ability to discriminate. The findings yield insight into the prospects and
limitations of MBDoE for TAP and transient kinetic experiments.
