Engineering topics

Danilack, Aaron D.

Publications and source records attributed to Danilack, Aaron D..

3 records

DOE OSTI2021

Non-Boltzmann Effects in Chain Branching and Pathway Branching for Diethyl Ether Oxidation

Low-temperature (LT) engine applications have several potential benefits, including reduced emissions and increased efficiency. Attaining these benefits requires accurate kinetic modeling of LT chain branching, which depends heavily on ketohydroperoxide (KHP) decomposition. For diethyl ether (DEE), a promising biofuel, current estimates of the KHP decomposition rate constant are largely based on empirical fits to data. In this study, we investigate the most important KHP isomer in DEE LT oxidation by applying variable reaction coordinate transition state theory to the main pathway for KHP decomposition: OO bond fission to produce •OH and a keto-alkoxy radical, •OQ'O. We also use ab initio kinetics methods to investigate the decomposition of •OQ'O, where we find dominant branching to acetic acid, with the remaining flux going to CH 3 C(O)OCHO. Additionally, new time-resolved measurements of DEE and acetic acid concentrations during LT (450–600 K) DEE oxidation are obtained in a laser photolysis flow reactor coupled with multiplexed photoionization mass spectrometry. These new experimental data, along with jet-stirred reactor data in the literature, are compared with the predictions of a recent DEE mechanism (Tran et al. Proc. Comb. Inst. 2019, 37, 511-519) that was modified with the newly calculated ab initio rate constants for KHP and •OQ'O decomposition. The predictions of the modified mechanism are quite poor when compared to the experimental data; this is primarily due to the new KHP ⇌ •OQ'O + •OH rate constant, which is 1–2 orders of magnitude slower than empirical values employed in recent mechanisms. To reconcile the new KHP rate constant and the experimental data, we explore and quantify the possible role of non-Boltzmann (nB) reaction sequences. The nB reactions have a substantial effect on both the overall mechanism reactivity and the •OQ'O branching to acetic acid. We also provide guidance on the proper implementation of nB reactions in kinetic mechanisms.

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DOE OSTI2021

Diastereomers and Low-Temperature Oxidation

Diastereomers have historically been ignored when building kinetic mechanisms for combustion. Low-temperature oxidation kinetics, which continues to gain interest in both combustion and atmospheric communities, may be affected by the inclusion of diastereomers in radical chain-branching pathways. In this work, key intermediates and transition states lacking stereochemical specification in an existing diethyl ether low-temperature oxidation mechanism were replaced with their diastereomeric counterparts. Rate coefficients for reactions involving diastereomers were computed with ab initio transition state theory master equation calculations. The presence of diastereomers increased rate coefficients by factors of 1.2-1.6 across various temperatures and pressures. Ignition delay simulations incorporating these revised rate coefficients indicate that the diastereomers enhanced the overall reactivity of the mechanism by almost 15% and increased the peak ketohydroperoxide concentration by 30% in the negative temperature coefficient region at combustion-relevant pressures. Furthermore, these results provide an illustrative indication of the important role of stereomeric effects in oxidation kinetics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

A statistical model for the product energy distribution in reactions leading to prompt dissociation

Direct dynamics calculations have been performed for three reactions: C 3 H 8 + H → i-C 3 H 7 + H 2 , C 3 H 8 + H → n-C 3 H 7 + H 2 , and C 2 H 3 + O 2 → HCO + CH 2 O. The fraction of the population for the radical products that promptly dissociates is computed. Here the results for C 3 H 8 + H are qualitatively similar to previous results for C 3 H 8 + OH, but the new results exhibit a slightly higher branching fraction for prompt dissociation products, owing to the fact that a greater fraction of the internal energy in the transition state ends up in the radical. For C 2 H 3 + O 2 → HCO + CH 2 O, the fraction of HCO that promptly dissociates is in excess of 99%. Consequently, the main product for C 2 H 3 + O 2 at lower temperatures should be written as H + CO + CH 2 O and not HCO + CH 2 O. These results are then compared with four previous systems: CH 2 O + H → HCO + H 2 , CH 2 O + OH → HCO + H 2 O, C 3 H 8 + OH → i-C 3 H 7 + H 2 O, and C 3 H 8 + OH → n-C 3 H 7 + H 2 O. Based upon these seven system, several statistical models are presented. The goal of these statistical models is to predict the fraction of the transition state energy that ends up in the rovibrationally excited radical. On average, these statistical models provide an excellent prediction of product energy distribution. Consequently, these models can be used instead of costly trajectory simulations for predicting prompt radical dissociation for larger species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗