Engineering Papers⌕ Search

Engineering topics

Sheps, Leonid

Publications and source records attributed to Sheps, Leonid.

33 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Formation of Organic Acids and Carbonyl Compounds in $\textit{n}$-Butane Oxidation via γ-Ketohydroperoxide Decomposition

A crucial chain-branching step in autoignition is the decomposition of ketohydroperoxides (KHP) to form an oxy radical and OH. Other pathways compete with chain-branching, such as “Korcek” dissociation of γ-KHP to a carbonyl and an acid. Here we characterize the formation of a γ-KHP and its decomposition to formic acid+acetone products from observations of $\textit{n}$-butane oxidation in two complementary experiments. In jet-stirred reactor measurements, KHP is observed above 590 K. The KHP concentration decreases with increasing temperature, whereas formic acid and acetone products increase. Observation of characteristic isotopologs acetone-$d_3$ and formic acid-$d_0$ in the oxidation of CH 3 CD 2 CD 2 CH 3 is consistent with a Korcek mechanism. In laser-initiated oxidation experiments of $\textit{n}$-butane, formic acid and acetone are produced on the timescale of KHP removal. Further, modelling the time-resolved production of formic acid provides an estimated upper limit of 2 s –1 for the rate coefficient of KHP decomposition to formic acid+acetone.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Prospects and Limitations of Predicting Fuel Ignition Properties from Low-Temperature Speciation Data

Using chemical kinetic modeling and statistical analysis, we investigate the possibility of correlating key chemical “markers”–typically small molecules–formed during very lean (φ ~ 0.001) oxidation experiments with near-stoichiometric (φ ~ 1) fuel ignition properties. One goal of this work is to evaluate the feasibility of designing a fuel-screening platform, based on small laboratory reactors that operate at low temperatures and use minimal fuel volume. Buras et al. [Combust. Flame2020,216, 472–484] have shown that convolutional neural net (CNN) fitting can be used to correlate first-stage ignition delay times (IDTs) with OH/HO2 measurements during very lean oxidation in low-T flow reactors with better than factor-of-2 accuracy. In this work, we test the limits of applying this correlation-based approach to predict the low-temperature heat release (LTHR) and total IDT, including the sensitivity of total IDT to the equivalence ratio, φ. We demonstrate that first-stage IDT can be reliably correlated with very lean oxidation measurements using compressed sensing (CS), which is simpler to implement than CNN fitting. LTHR can also be predicted via CS analysis, although the correlation quality is somewhat lower than for first-stage IDT. In contrast, the accuracy of total IDT prediction at φ = 1 is significantly lower (within a factor of 4 or worse). Furthermore, these results can be rationalized by the fact that the first-stage IDT and LTHR are primarily determined by low-temperature chemistry, whereas total IDT depends on low-, intermediate-, and high-temperature chemistry. Oxidation reactions are most important at low temperatures, and therefore, measurements of universal molecular markers of oxidation do not capture the full chemical complexity required to accurately predict the total IDT even at a single equivalence ratio. As a result, we find that φ-sensitivity of ignition delay cannot be predicted at all using solely correlation with lean low-T chemical speciation measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Insertion products in the reaction of carbonyl oxide Criegee intermediates with acids: Chloro(hydroperoxy)methane formation from reaction of CH 2 OO with HCl and DCl

The reactions of carbonyl oxides (“Criegee intermediates”) with organic and inorganic acids have been postulated to proceed predominantly by an insertion mechanism, and the hydroperoxy-substituted ester products from reactions with organic acids have been spectroscopically observed. Here this work characterizes the products from one of the simplest reactions of carbonyl oxides with inorganic acids, that of formaldehyde oxide, CH 2 OO, with hydrogen chloride, which occurs via a 1,2-insertion in the H–Cl bond. Reactions of both HCl and DCl isotopologues yield product signal at the mass of the insertion product chloro(hydroperoxy)methane and a dissociative ionisation peak at the mass of the protonated (or deuteronated) Criegee intermediate. The isotopic composition of the insertion product has been measured for reaction mixtures where both HCl isotopologues are present, and the H/D ratio of the product is consistently higher (by a factor of 1.6 ± 0.3) than that of the reactants. This isotope selectivity in the products has smaller uncertainty than the ratio of measured rate coefficients and suggests a normal (k H > k D ) kinetic isotope effect in the reaction. Theoretical kinetics calculations predict a small normal kinetic isotope effect for the overall reaction (k H / k D = 1.35 at 20 Torr N 2 and k H / k D = 1.2 for 1 atm N 2 ) but predict a substantial inverse kinetic isotope effect (k D > k H ) for the stabilisation fraction, in disagreement with the experimental observation.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Table-Top High Photon Energy Sources for Chemical Dynamics Investigations

Time-resolved spectroscopies using high-energy photons in the vacuum ultraviolet (VUV) to the X-ray region of the electromagnetic spectrum, have proven to be powerful probes of chemical dynamics. These high-energy photons can access valence and core orbitals of molecules and materials, providing key information on molecular and electronic structure and their time evolution. This report details the development of table-top sources of extreme ultraviolet (XUV) and VUV pulses at Sandia National Laboratories for use in studies of gas phase chemical dynamics. Femtosecond duration XUV pulses are produced using laser-driven high harmonic generation and their detected range span ~40-140 eV photon energies. These pulses are used in conjunction with ultraviolet pulses in a pump-probe scheme to study excited state dynamics of gas phase molecules. VUV pulses at 7.75 eV are generated using a four-wave-mixing scheme driven by 800 nm and 266 nm pulses in an argon-filled hollow-core fiber.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

A New Approach to Fundamental Mechanism Discovery in Polymer Upcycling

We present a new experimental methodology for detailed experimental investigations of depolymerization reactions over solid catalysts. This project aims to address a critical need in fundamental research on chemical upcycling of polymers – the lack of rapid, sensitive, isomerselective probing techniques for the detection of reaction intermediates and products. Our method combines a heterogeneous catalysis reactor for the study of multiphase (gas/polymer melt/solid) systems, coupled to a vacuum UV photoionization time-of-flight mass spectrometer. This apparatus draws on our expertise in probing complex gas-phase chemistry and enables highthroughput, detailed chemical speciation measurements of the gas phase above the catalyst, providing valuable information on the heterogeneous catalytic reactions. Using this approach, we investigated the depolymerization of high-density polyethylene (HDPE) over Ir-doped zeolite catalysts. We showed that the product distribution was dominated by low-molecular weight alkenes with terminal C=C double bonds and revealed the presence of many methyl-substituted alkenes and alkanes, suggesting extensive methyl radical chemistry. In addition, we investigated the fundamental reactivity of model oligomer molecules n-butane and isobutane over ZSM-5 zeolites. We demonstrated the first direct detection of methyl radical intermediates, confirming the key role of methyl in zeolite-catalyzed activation of alkanes. Our results show the potential of this experimental method to achieve deep insight into the complex depolymerization reactions and pave the way for detailed mechanistic studies, leading to increased fundamental understanding of key processes in chemical upcycling of polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗