Comprehensive reevaluation of acetaldehyde chemistry and the underlying uncertainties

TL;DR

This paper thoroughly reevaluates acetaldehyde combustion chemistry by updating key reaction rates and thermodynamic data through extensive experiments and computations, leading to improved models especially at high temperatures.

Contribution

It provides a comprehensive reassessment of acetaldehyde reaction rates and thermochemistry, integrating experimental and theoretical data for more accurate combustion models.

Findings

Enhanced model performance at high temperatures.

Identification of key pathway deficiencies in previous models.

Quantified uncertainties in kinetic and thermochemical parameters.

Abstract

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 reevaluate the important rate and thermodynamic parameters for acetaldehyde combustion chemistry. The rate parameters of 79 key reactions are reevaluated using more than 100,000 direct experiments and quantum chemistry computations from >900 studies, and the thermochemistry ({\Delta}hf(298K), s0(298K) 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 (123 ignition delay times and 385 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. 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.