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Parametrization and Cartesian representation techniques for robust resolution of chemical equilibria

Title: Parametrization and Cartesian representation techniques for robust resolution of chemical equilibria
Authors: Jonval, Maxime; Ben Gharbia, Ibtihel; Cancès, Clément; Faney, Thibault; Tran, Quang Huy
Contributors: IFP Energies nouvelles (IFPEN); Reliable numerical approximations of dissipative systems (RAPSODI); Laboratoire Paul Painlevé - UMR 8524 (LPP); Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Centre Inria de l'Université de Lille; Institut National de Recherche en Informatique et en Automatique (Inria)-Institut National de Recherche en Informatique et en Automatique (Inria); This work was jointly supported by IFPEN and Inria.; ANR-23-EXMA-0010,MATHSOUT,Mathématiques Souterraines(2023); ANR-11-LABX-0007,CEMPI,Centre Européen pour les Mathématiques, la Physique et leurs Interactions(2011)
Source: ISSN: 0021-9991.
Publisher Information: CCSD; Elsevier
Publication Year: 2025
Collection: LillOA (HAL Lille Open Archive, Université de Lille)
Subject Terms: Chemical equilibria; Newton's method; Parametrization; Cartesian representation; [MATH.MATH-NA]Mathematics [math]/Numerical Analysis [math.NA]; [CHIM]Chemical Sciences
Description: International audience ; Chemical equilibria computations, especially those with vanishing species in the aqueous phase, lead to nonlinear systems that are difficult to solve due to gradient blow up. Instead of the commonly used ad hoc treatments, we propose two reformulations of the single-phase chemical equilibrium problem which are in line with the spirit of preconditioning but whose actual aims are to guarantee a better stability of Newton's method. The first reformulation is a parametrization of the graph linking species mole fractions to their chemical potentials. The second is based on an augmented system where this relationship is relaxed for the iterates by means of a Cartesian representation. We theoretically prove the local quadratic convergence of Newton's method for both reformulations. From a numerical point of view, we demonstrate that the two techniques are accurate, allowing to compute equilibria with chemical species having very low concentrations. Moreover, the robustness of our methods combined with a globalization strategy is superior to that of the literature.
Document Type: article in journal/newspaper
Language: English
DOI: 10.1016/j.jcp.2024.113596
Availability: https://hal.science/hal-04225504; https://hal.science/hal-04225504v3/document; https://hal.science/hal-04225504v3/file/main.pdf; https://doi.org/10.1016/j.jcp.2024.113596
Rights: info:eu-repo/semantics/OpenAccess
Accession Number: edsbas.864273D3
Database: BASE