In many studies, kinetic parameter estimation from spectroscopic data is performed with the absorbing species known beforehand, as this provides a straightforward link between the reaction models to the spectroscopic data. In practice, however, the absorbing species are generally unknown and they are only estimated based on professional experience and prior knowledge of the kinetic reaction. In this work, we propose an optimization strategy with both continuous and discrete decision variables in order to estimate kinetic parameters from spectroscopic data with unknown absorbing species. Also included in our approach is an estimability analysis for kinetic parameters based on the Gram‐Schmidt orthogonalization procedure, along with covariance estimation. Four case studies were considered, which demonstrate the effectiveness of our approach. The first and second have simulated data and illustrate our approach with known solutions. The third and fourth are based on actual experiments from spectroscopy data sets. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3595–3613, 2018

中文翻译：

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基于未知吸收光谱数据的动力学参数估计

在许多研究中，利用事先已知的吸收物种从光谱数据估算动力学参数，因为这提供了反应模型与光谱数据之间的直接联系。然而，实际上，吸收物质通常是未知的，并且仅基于专业经验和动力学反应的先验知识进行估算。在这项工作中，我们提出了一个具有连续和离散决策变量的优化策略，以便从具有未知吸收物种的光谱数据中估算动力学参数。我们的方法中还包括基于Gram-Schmidt正交化程序的动力学参数的可估计性分析以及协方差估计。考虑了四个案例研究，这些案例证明了我们方法的有效性。第一个和第二个具有模拟数据，并用已知的解决方案说明了我们的方法。第三和第四是基于光谱数据集的实际实验。©2018美国化学工程师学会AIChE J，64：3595–3613，2018