Titre :

Reaction rate ambiguities for perturbed spectroscopic data: Theory and implementation.

Auteur(s) :

Schröder, H. [Auteur]
Ruckebusch, Cyril [Auteur]
Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement (LASIRE) - UMR 8516
Brächer, A. [Auteur]
Sawall, M. [Auteur]
Meinhardt, D. [Auteur]
Kubis, C. [Auteur]
Mostafapour, S. [Auteur]
Börner, A. [Auteur]
Franke, R. [Auteur]
Neymeyr, K. [Auteur]

Titre de la revue :

Analytica Chimica Acta

Nom court de la revue :

Anal Chim Acta

Numéro :

1137

Pagination :

170-180

Date de publication :

2020-11-11

ISSN :

1873-4324

Mot(s)-clé(s) en anglais :

Nonnegative matrix factorization
Factor analysis
Ambiguity of rate constants
identifiability
Kinetic modeling
Spectral recovery

Discipline(s) HAL :

Chimie/Chimie théorique et/ou physique

Résumé en anglais : [en]

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 ...
Lire la suite >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.Lire moins >

Langue :

Anglais

Comité de lecture :

Oui

Audience :

Internationale

Vulgarisation :

Non

Établissement(s) :

Université de Lille
CNRS

Collections :

• Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement (LASIRE) - UMR 8516

Date de dépôt :

2024-02-28T22:50:25Z
2024-03-12T09:52:06Z