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.

翻译：产物时间分析（TAP）反应器能够通过改变脉冲强度、延迟或温度，在单组实验数据中探测多种动力学过程。选择额外的TAP实验通常依赖于实验条件的任意选取或化学直觉。为增强TAP实验选择的鲁棒性，我们探索了基于模型的实验设计（MBDoE）在TAP反应器动力学建模中的精确性有效性。我们将该方法成功应用于涉及丙烷和氧气脉冲的合成氧化丙烷脱氢（OPDH）案例研究中。研究发现，通过MBDoE选择的最优实验通常能比替代实验更高程度地降低参数不确定性。同时，针对活性位点（催化剂结构）未知的OPDH体系，我们探索了MBDoE在模型区分中的性能。研究确定了一种能最大化三种机理模型差异的实验方案，实现了明确的机理判别。然而，动力学参数的重新优化削弱了模型区分能力。这些发现揭示了MBDoE在TAP及瞬态动力学实验中的应用前景与局限性。