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As crucial additives and intermediate, alcohols, ethers, and aldehydes play a significant role in the combustion process. However, the chemistry of NOXhydrocarbon interactions and the rate rules governing these interactions remain largely unexplored in this combustion system. To address this gap, this study provides a comprehensive investigation of H-atom abstraction by NO2 from C1-C4 alcohols, aldehydes and ethers that leads to the formation of 3 HNO2 isomers (i.e., transHONO, HNO2, and cisHONO), encompassing 9 hydrocarbons and 45 reactions. Utilizing the DLPNO CCSD(T)cc pVDZ M06 2X 6 311g d,p method, the electronic structures, single point energies, C H bond dissociation energies and 1 D hindered rotor potentials of the reactants, transition states, complexes and products in each reaction are computed. Adding these H atom abstractions to the chemical kinetic model improves the model reactivity and advances the ignition, as indicated by the reduction in ignition delay time for species that initially lacked these reactions. Further sensitivity and flux analyses highlight the crucial role of H atom abstraction by NO2. The findings underscore the importance of accurately incorporating these kinetic parameters into newly developed chemical models for alcohols, aldehydes, and ethers. Additionally, the study highlights the need for future experimental efforts to investigate the effects of NO2 on the combustion systems of these compounds., Comment: 52 pages

Significant efforts have been committed to understanding the fundamental combustion chemistry of ammonia at high-pressure and low-temperature conditions with or without blending with other fuels, as these are promising to improve ammonia combustion performance and reduce NOx emission. A commonly used fundamental reactor is the jet-stirred reactor (JSR). However, modeling of high-pressure JSR experiments have been conducted assuming complete ideal gas behaviors, which might lead to misinterpreted or completely wrong results. Therefore, this study proposes, for the first time, a novel framework coupling high-order Virial equation of state, ab initio multi-body intermolecular potential, and real-fluid governing equations. The framework is further applied to investigate NH$_3$ oxidation under supercritical conditions in jet-stirred reactors, where the real-fluid effects on NH$_3$ oxidation characteristics are quantified and compared, via simulated species profiles and relative changes in simulated mole fractions, at various temperatures, pressures, dilution ratios, equivalence ratios, and with or without blending with H$_2$ and CH$_4$. Strong promoting effects on NH$_3$ oxidation from real-fluid effects are revealed, with significant shifts in simulated species profiles observed for both fuel, intermediates and product species. Sensitivity analyses are also conducted based on the new framework, with diverse influences of real-fluid effects on the contributions of the most sensitive pathways highlighted. It is found that, without considering real-fluid behaviors, the error introduced in simulated species mole fractions can reach 85% at the conditions investigated in this study. Propagation of such levels of error to chemical kinetic mechanisms can disqualify them for any meaningful modeling work. These errors can now be excluded using the framework developed in this study.

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.

Supercritical oxidation processes in jet-stirred reactors (JSR) have been modeled based on ideal gas assumption. This can lead to significant errors in or complete misinterpretation of modeling results. Therefore, this study newly developed a framework to model supercritical oxidation in JSRs by incorporating ab initio multi-body molecular potentials and high-order mixture Virial equation of state (EoS) into real-fluid conservation laws, with the related numerical strategies highlighted. With comparisons with the simulation results based on ideal EoS and the experimental data from high-pressure JSR experiments, the framework is proved to be a step forward compared to the existing JSR modeling frameworks. To reveal the real-fluid effects on the oxidation characteristics in jet-stirred reactors, simulations are further conducted at a wide range of conditions (i.e., temperatures from 500 to 1100 K and pressures from 100 to 1000 bar), the real-fluid effect is found to significantly promote fuel oxidation reactivity, especially at low temperatures, high pressures, and for mixtures with heavy fuels. The significant influences of real-fluid behaviors on JSR oxidation characteristics emphasize the need to adequately incorporate these effects for future modeling studies in JSR at high pressures, which has now been enabled through the framework proposed in this study.

An adequate understanding of NOx interacting chemistry is a prerequisite for a smoother transition to carbon lean and carbon free fuels such as ammonia and hydrogen. In this regard, this study presents a comprehensive study on the H atom abstraction by NO2 from C3 to C7 alkynes and dienes forming 3 HNO2 isomers (i.e., TRANS HONO, HNO2, and CIS HONO), encompassing 8 hydrocarbons and 24 reactions. Through a combination of high level quantum chemistry computation, the rate coefficients for all studied reactions, over a temperature range from 298 to 2000 K, are computed based on Transition State Theory using the Master Equation System Solver program with considering unsymmetric tunneling corrections. Comprehensive analysis of branching ratios elucidates the diversity and similarities between different species, different HNO2 isomers, and different abstraction sites. Incorporating the calculated rate parameters into a recent chemistry model reveals the significant influences of this type of reaction on model performance, where the updated model is consistently more reactive for all the alkynes and dienes studied in predicting autoignition characteristics. Sensitivity and flux analyses are further conducted, through which the importance of H atom abstractions by NO2 is highlighted. With the updated rate parameters, the branching ratios in fuel consumption clearly shifts towards H atom abstractions by NO2 while away from H atom abstractions by OH. The obtained results emphasize the need for adequately representing these kinetics in new alkyne and diene chemistry models to be developed by using the rate parameters determined in this study, and call for future efforts to experimentally investigate NO2 blending effects on alkynes and dienes., Comment: 33 pages. arXiv admin note: text overlap with arXiv:2408.15023

This study aims to reveal the important role and the respective rate rules of H atom abstractions by NO2 for better understanding NOX hydrocarbon interactions. To this end, H atom abstractions from C2 to C5 alkanes and alkenes 15 species by NO2, leading to the formation of three HNO2 isomers (TRANS HONO, HNO2, and CIS HONO) and their respective products 45 reactions, are first characterized through high-level quantum chemistry computation, where electronic structures, single point energies, C H bond dissociation energies and 1 D hindered rotor potentials are determined at DLPNO CCSD T cc pVDZ M06 2X 6 311 plus plus g(d,p). The rate coefficients for all studied reactions, over a temperature range from 298.15 to 2000 K, are computed using Transition State Theory with the Master Equation System Solver program. Comprehensive analysis of branching ratios elucidates the diversity and similarities between different species, HNO2 isomers, and abstraction site, from which accurate rate rules are determined. Incorporating the updated rate parameters into a detailed chemical kinetic model reveals the significant influences of this type of reaction on model prediction results, where the simulated ignition delay times are either prolonged or reduced, depending on the original rate parameters presented in the selected model. Sensitivity and flux analysis further highlight the critical role of this type of reaction in affecting system reactivity and reaction pathways, emphasizing the need for adequately representing these kinetics in existing chemistry models. This can now be sufficiently achieved for alkanes and alkenes through the results from this study., Comment: 33 pages