Title :

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

Author(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]

Journal title :

Analytica Chimica Acta

Abbreviated title :

Anal Chim Acta

Volume number :

1137

Pages :

170-180

Publication date :

2020-11-11

ISSN :

1873-4324

English keyword(s) :

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

HAL domain(s) :

Chimie/Chimie théorique et/ou physique

English abstract : [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 ...
Show more >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.Show less >

Language :

Anglais

Peer reviewed article :

Oui

Audience :

Internationale

Popular science :

Non

Administrative institution(s) :

Université de Lille
CNRS

Collections :

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

Submission date :

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