乙醛化学及其潜在不确定性的全面重新评估
Comprehensive reevaluation of acetaldehyde chemistry and the underlying uncertainties
AI总结：
本研究综合大量直接实验、量子化学计算及数据库，系统重估乙醛燃烧的79个反应速率参数、24种物种热化学参数及其不确定性，显著提升模型高温预测表现。
摘要：
理解乙醛的燃烧化学对于为实际燃料（尤其是生物燃料）开发稳健且准确的燃烧化学模型至关重要。本研究旨在重新评估乙醛燃烧化学的重要速率参数和热力学参数。研究利用来自900多项研究的超过100,000项直接实验和量子化学计算，重新评估了79个关键反应的速率参数；并基于ATCT数据库、NIST Chemistry WebBook、TMTD数据库以及35个已发表的化学模型，重新评估了24种关键物种的热化学性质（Δhf(298K)、s0(298K)和cp）。更新后的参数被纳入一个近期的乙醛化学模型，并进一步依据现有基础实验（123个点火延迟时间和385个物种浓度）及已有化学模型进行评估，结果表明其在高温区间取得了明显更优的性能。敏感性分析和通量分析进一步凸显了以往模型在表征关键路径方面的不足，尤其是消耗乙醛和甲醛路径的分支比。研究分别对动力学参数和热化学参数的温度相关不确定性与温度无关不确定性进行了统计评估；更新参数与原始模型参数之间的巨大差异表明，有必要完全依据速率参数和热力学参数的直接实验与理论计算，对动力学和热化学参数进行重新评估。
英文摘要：
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 (Δhf(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.
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