The analysis of reaction systems and their kinetic modeling is important for both exploratory research and process design. Multivariate curve resolution (MCR) methods are state-of-the-art tools for the analysis of spectral series, but are also affected by an unavoidable solution ambiguity that impacts the obtained concentration profiles, spectra and model parameters. These uncertainties depend on the underlying model and the magnitude of the measurement perturbations. We present a general theoretical approach together with a computational method for the analysis of the solution ambiguity underlying arbitrary kinetic models. The main idea is to determine all those model parameters for which the corresponding pure component factorizations satisfy all given constraints within small error tolerances. This makes it possible to determine bands of concentration profiles and spectra that reflect the underlying ambiguity and circumscribes the potential reliability of MCR solutions. False conclusions on the uniqueness of a solution can be prevented. The procedure can be applied as a post-processing step to MCR methods as MCR-ALS, ReactLab or others. The Matlab program code is freely accessible and includes not only the proposed ambiguity analysis but also an MCR hard-modeling approach. Application studies are presented for two experimental data sets, namely for UV/Vis spectra on the relaxation of a photoexcited state of benzophenone and for Raman spectra on an aldehyde formation process.

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扰动光谱数据的反应速率模糊：理论与实现

反应系统及其动力学模型的分析对于探索性研究和工艺设计都很重要。多元曲线分辨率 (MCR) 方法是用于光谱系列分析的最先进工具，但也受到不可避免的解模糊度的影响，该模糊度会影响获得的浓度分布、光谱和模型参数。这些不确定性取决于基础模型和测量扰动的幅度。我们提出了一种通用的理论方法和一种计算方法，用于分析基于任意动力学模型的解决方案模糊性。主要思想是确定相应的纯分量分解满足小误差容限内的所有给定约束的所有模型参数。这使得可以确定反映潜在模糊性并限制 MCR 解决方案潜在可靠性的浓度曲线和光谱带。可以防止对解决方案唯一性的错误结论。该程序可作为 MCR-ALS、ReactLab 或其他 MCR 方法的后处理步骤。Matlab 程序代码可免费访问，不仅包括建议的歧义分析，还包括 MCR 硬建模方法。介绍了两个实验数据集的应用研究，即二苯甲酮光激发态弛豫的紫外/可见光谱和醛形成过程的拉曼光谱。可以防止对解决方案唯一性的错误结论。该程序可作为 MCR-ALS、ReactLab 或其他 MCR 方法的后处理步骤。Matlab 程序代码可免费访问，不仅包括建议的歧义分析，还包括 MCR 硬建模方法。介绍了两个实验数据集的应用研究，即二苯甲酮光激发态弛豫的紫外/可见光谱和醛形成过程的拉曼光谱。可以防止对解决方案唯一性的错误结论。该程序可作为 MCR-ALS、ReactLab 或其他 MCR 方法的后处理步骤。Matlab 程序代码可免费访问，不仅包括建议的歧义分析，还包括 MCR 硬建模方法。介绍了两个实验数据集的应用研究，即二苯甲酮光激发态弛豫的紫外/可见光谱和醛形成过程的拉曼光谱。