Comprehensive reevaluation of acetaldehyde chemistry - part I: Assessment of important kinetic parameters and the underlying uncertainties

Understanding the combustion chemistry of acetaldehyde is crucial to developing robust and accurate combustion chemistry models for practical fuels, especially for biofuels. This study aims to re-evaluate the important rate and thermodynamic parameters for acetaldehyde combustion chemistry and deter...

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Main Authors: Xinrui Ren, Hongqing Wu, Ruoyue Tang, Yanqing Cui, Mingrui Wang, Song Cheng
Format: Article
Language:English
Published: Elsevier 2025-03-01
Series:Applications in Energy and Combustion Science
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Online Access:http://www.sciencedirect.com/science/article/pii/S2666352X25000020
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author Xinrui Ren
Hongqing Wu
Ruoyue Tang
Yanqing Cui
Mingrui Wang
Song Cheng
author_facet Xinrui Ren
Hongqing Wu
Ruoyue Tang
Yanqing Cui
Mingrui Wang
Song Cheng
author_sort Xinrui Ren
collection DOAJ
description Understanding the combustion chemistry of acetaldehyde is crucial to developing robust and accurate combustion chemistry models for practical fuels, especially for biofuels. This study aims to re-evaluate the important rate and thermodynamic parameters for acetaldehyde combustion chemistry and determine the physical uncertainties of these parameters. The rate parameters of 79 key reactions are reevaluated using > 100,000 direct experiments and quantum chemistry computations from > 900 studies, and the thermochemistry (Δhf(298 K), s0(298 K) and cp) of 24 key species are reevaluated based on the ATCT database, the NIST Chemistry WebBook, the TMTD database, and 35 published chemistry models. The updated parameters are incorporated into a recent acetaldehyde chemistry model, which is further assessed against available fundamental experiments measurements (10 RCM-IDT, 123 ST-IDT, 633 JSR-species concentrations, and 102 flow reactor-species concentrations) and existing chemistry models, with clearly better performance obtained in the high-temperature regime. Sensitivity and flux analyses further highlight the insufficiencies of previous models in representing the key pathways, particularly the branching ratios of acetaldehyde- and formaldehyde-consuming pathways. Meanwhile, temperature-dependent and temperature-independent uncertainties are statistically evaluated for kinetic and thermochemical parameters, respectively, where the large differences between the updated and the original model parameters reveal the necessity of reassessment of kinetic and thermochemical parameters completely based on direct experiments and theoretical calculations for rate and thermodynamic parameters. The application of the determined uncertainty domains of the key kinetic and thermodynamic parameters is further demonstrated through a case study, with the modelling uncertainty and its reliability highlighted. With the configured uncertainty domain of the updated acetaldehyde chemistry model, further uncertainty quantification and optimization can be conducted to improve the model performance, which is currently under progress in the authors’ group.
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spelling doaj-art-e964f1b066be429b86d058023e514c1d2025-08-20T03:02:06ZengElsevierApplications in Energy and Combustion Science2666-352X2025-03-012110032010.1016/j.jaecs.2025.100320Comprehensive reevaluation of acetaldehyde chemistry - part I: Assessment of important kinetic parameters and the underlying uncertaintiesXinrui Ren0Hongqing Wu1Ruoyue Tang2Yanqing Cui3Mingrui Wang4Song Cheng5Department of Mechanical Engineering, The Hong Kong Polytechnic University, Kowloon 999077, Hong KongDepartment of Mechanical Engineering, The Hong Kong Polytechnic University, Kowloon 999077, Hong KongDepartment of Mechanical Engineering, The Hong Kong Polytechnic University, Kowloon 999077, Hong KongDepartment of Mechanical Engineering, The Hong Kong Polytechnic University, Kowloon 999077, Hong KongDepartment of Mechanical Engineering, The Hong Kong Polytechnic University, Kowloon 999077, Hong KongDepartment of Mechanical Engineering, The Hong Kong Polytechnic University, Kowloon 999077, Hong Kong; Research Institute for Smart Energy, The Hong Kong Polytechnic University, Kowloon 999077, Hong Kong; Corresponding authors at: Department of Mechanical Engineering, The Hong Kong Polytechnic University, Kowloon 999077, Hong Kong.Understanding the combustion chemistry of acetaldehyde is crucial to developing robust and accurate combustion chemistry models for practical fuels, especially for biofuels. This study aims to re-evaluate the important rate and thermodynamic parameters for acetaldehyde combustion chemistry and determine the physical uncertainties of these parameters. The rate parameters of 79 key reactions are reevaluated using > 100,000 direct experiments and quantum chemistry computations from > 900 studies, and the thermochemistry (Δhf(298 K), s0(298 K) and cp) of 24 key species are reevaluated based on the ATCT database, the NIST Chemistry WebBook, the TMTD database, and 35 published chemistry models. The updated parameters are incorporated into a recent acetaldehyde chemistry model, which is further assessed against available fundamental experiments measurements (10 RCM-IDT, 123 ST-IDT, 633 JSR-species concentrations, and 102 flow reactor-species concentrations) and existing chemistry models, with clearly better performance obtained in the high-temperature regime. Sensitivity and flux analyses further highlight the insufficiencies of previous models in representing the key pathways, particularly the branching ratios of acetaldehyde- and formaldehyde-consuming pathways. Meanwhile, temperature-dependent and temperature-independent uncertainties are statistically evaluated for kinetic and thermochemical parameters, respectively, where the large differences between the updated and the original model parameters reveal the necessity of reassessment of kinetic and thermochemical parameters completely based on direct experiments and theoretical calculations for rate and thermodynamic parameters. The application of the determined uncertainty domains of the key kinetic and thermodynamic parameters is further demonstrated through a case study, with the modelling uncertainty and its reliability highlighted. With the configured uncertainty domain of the updated acetaldehyde chemistry model, further uncertainty quantification and optimization can be conducted to improve the model performance, which is currently under progress in the authors’ group.http://www.sciencedirect.com/science/article/pii/S2666352X25000020Acetaldehyde chemistryPhysics-based model reevaluationModel validation and comparisonUncertainty analysis
spellingShingle Xinrui Ren
Hongqing Wu
Ruoyue Tang
Yanqing Cui
Mingrui Wang
Song Cheng
Comprehensive reevaluation of acetaldehyde chemistry - part I: Assessment of important kinetic parameters and the underlying uncertainties
Applications in Energy and Combustion Science
Acetaldehyde chemistry
Physics-based model reevaluation
Model validation and comparison
Uncertainty analysis
title Comprehensive reevaluation of acetaldehyde chemistry - part I: Assessment of important kinetic parameters and the underlying uncertainties
title_full Comprehensive reevaluation of acetaldehyde chemistry - part I: Assessment of important kinetic parameters and the underlying uncertainties
title_fullStr Comprehensive reevaluation of acetaldehyde chemistry - part I: Assessment of important kinetic parameters and the underlying uncertainties
title_full_unstemmed Comprehensive reevaluation of acetaldehyde chemistry - part I: Assessment of important kinetic parameters and the underlying uncertainties
title_short Comprehensive reevaluation of acetaldehyde chemistry - part I: Assessment of important kinetic parameters and the underlying uncertainties
title_sort comprehensive reevaluation of acetaldehyde chemistry part i assessment of important kinetic parameters and the underlying uncertainties
topic Acetaldehyde chemistry
Physics-based model reevaluation
Model validation and comparison
Uncertainty analysis
url http://www.sciencedirect.com/science/article/pii/S2666352X25000020
work_keys_str_mv AT xinruiren comprehensivereevaluationofacetaldehydechemistrypartiassessmentofimportantkineticparametersandtheunderlyinguncertainties
AT hongqingwu comprehensivereevaluationofacetaldehydechemistrypartiassessmentofimportantkineticparametersandtheunderlyinguncertainties
AT ruoyuetang comprehensivereevaluationofacetaldehydechemistrypartiassessmentofimportantkineticparametersandtheunderlyinguncertainties
AT yanqingcui comprehensivereevaluationofacetaldehydechemistrypartiassessmentofimportantkineticparametersandtheunderlyinguncertainties
AT mingruiwang comprehensivereevaluationofacetaldehydechemistrypartiassessmentofimportantkineticparametersandtheunderlyinguncertainties
AT songcheng comprehensivereevaluationofacetaldehydechemistrypartiassessmentofimportantkineticparametersandtheunderlyinguncertainties