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DOE OSTI2025

Measured Reaction Rate Ratios of 235 U, 238 U, 237 Np, 239 Pu Samples in the PFUNS 235 U Prompt Fission Neutron Spectrum Criticality Experiment

The Prompt Fission Uranium Neutron Spectrum experiment, an experiment to reduce uncertainties in the high energy tail of the 235 U prompt fission spectrum, achieved success by performing two separate irradiations measuring approximately 40 different IRDFF-II reactions total using over 20 different foil materials at the National Criticality Experiments Research Center in February 2024. The criticality experiment utilized a set of highly enriched uranium hemispherical shells of increasing diameters with a large void in the center where the samples were located. The focus of this work is the first of two PFUNS irradiations focused on irradiating two of each fission foils, one bare and one cadmium covered, along with metal activation foils containing reaction products with short half-lives, such as indium, iron, and gold along with nickel fluence monitors. This work focuses on presenting the initial reaction rate ratio results of the fission foils from the aforementioned first irradiation to assist in nuclear data validation of those species in a nearly pure 235 U prompt fission neutron spectrum and compares to the Lady Godiva and Flattop-25 historic experiments at the Los Alamos Critical Experiments Facility. Future work will combine fission foil and metallic activation foil reaction rate ratio results from both the first and second higher power irradiation and reaction rates for a final spectral adjustment.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2024

Solar enhanced oxygen evolution reaction with transition metal telluride

The photo-enhanced electrocatalytic method of oxygen evolution reaction (OER) shows promise for enhancing the effectiveness of clear energy generation through water splitting by using renewable and sustainable source of energy. However, despite benefits of photoelectrocatalytic (PEC) water splitting, its uses are constrained by its low efficiency as a result of charge carrier recombination, a large overpotential, and sluggish reaction kinetics. Here, we illustrate that Nickel telluride (NiTe) synthesized by hydrothermal methods can function as an extremely effective photo-coupled electrochemical oxygen evolution reaction (POER) catalyst. In this study, NiTe was synthesized by hydrothermal method at 145°C within just an hour of reaction time. In dark conditions, the NiTe deposited on carbon cloth substrate shows a small oxygen evolution reaction overpotential (261 mV) at a current density of 10 mA cm –2 , a reduced Tafel slope (65.4 mV dec -1 ), and negligible activity decay after 12 h of chronoamperometry. By virtue of its enhanced photo response, excellent light harvesting ability, and increased interfacial kinetics of charge separation, the NiTe electrode under simulated solar illumination displays exceptional photoelectrochemical performance exhibiting overpotential of 165 mV at current density of 10 mA cm -2 , which is about 96 mV less than on dark conditions. In addition, Density Functional Theory investigations have been carried out on the NiTe surface, the results of which demonstrated a greater adsorption energy for intermediate -OH on the catalyst site. Since the -OH adsorption on the catalyst site correlates to catalyst activation, it indicates the facile electrocatalytic activity of NiTe owing to favorable catalyst activation. DFT calculations also revealed the facile charge density redistribution following intermediate -OH adsorption on the NiTe surface. This work demonstrates that arrays of NiTe elongated nanostructure are a promising option for both electrochemical and photoelectrocatalytic water oxidation and offers broad suggestions for developing effective PEC devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Prospects for Neutron Reactions on Excited States in High-Density Plasmas

With the reactions of high flux neutrons, such as in a DT plasma, there is a prospect of seeing new kinds of neutron-nucleus reactions for the first time. If neutrons excite a heavy nucleus, for example, there is possibility of a second neutron reacting on excited states of the residual nucleus before that nucleus has de-excited to its ground state. The possibility of such reactions on excited states has rarely been considered. The cross section for neutron induced fission on the isomeric state of 235 U has been measured (D’Eer et al., Phys. Rev. C, 1988, 38: 1270–1276) and calculated (Younes et al., 2003, Maslov, 2007), and reactions on rotationally excited nuclear states has been calculated (Kawano et al., Phys. Rev. C, 2009, 80: 024611). In high flux plasmas, however, a much wider range of reactions is possible. We therefore need to consider excited states at much higher-energies than previously modeled, and then estimate whether second neutrons are likely to rescatter on those excited states. To determine the likelihood of such rescattering events, we first need to know the probable time series of nuclear decays of those excited states. The lifetimes of many low-lying states have been measured experimentally, but now we need to know the lifetimes of the many higher excited states that could be produced from incident 14 MeV neutrons. These are too numerous to be measured and also too numerous to be calculated individually, so statistical Hauser-Feshbach decay models are used. I show some lifetime calculations for 89 Y, 169 Tm, and 197 Au targets, and predictions for the number of rescattering events in plausible plasma scenarios.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2021

Correlated $\ n-γ$ angular distributions from the $\ Q$ = 4.4398 MeV 12 C ($\ n, n' γ$) reaction for incident neutron energies from 6.5 MeV to 16.5 MeV

Neutron scattering cross sections and angular distributions represent one of the most glaring sources of uncertainty in calculations of nuclear systems. Even simple nuclei like 12 C show indications of errors in nuclear databases for scattering reactions. Measurements of inelastic neutron scattering have historically measured either the scattered neutrons or the nuclear deexcitation $\ γ$ emission. Only a very small number of experiments attempted correlated measurements of both the neutron and $\ γ$ data simultaneously, even though these $\ n-γ$ correlations could be essential for understanding particle transport in nuclear systems. In this work we describe a measurement of the $\ n, γ$, and correlated $\ n-γ$ angular distributions from the $\ Q$ = 4.4398 MeV 12 C ($\ n, n'γ$) reaction in a single experiment using an EJ-309 liquid scintillator detector array with wide angular coverage, and with a continuous incident neutron energy range from 6.5 to 16.5 MeV. We also provide a thorough covariance description of these results, including normalization of the probability distribution. While the measured n distributions agree well with the relatively large number of available literature measurements, there are comparatively very few measurements of the γ distributions from this reaction. However, our data support the presence of a nonzero α 4 Legendre polynomial component of the γ angular distribution suggested in past measurements, which is currently not incorporated in the ENDF/B-VIII.0 library despite the use of these same literature data for evaluation of the 12 C ($\ n, n'γ$) cross section. The correlated $\ n-γ$ distribution measurements are limited to three measurements at incident neutron energies near 14 MeV. Our results do not generally agree with any of these literature measurements. We observe clear indications of significant changes in the $\ n$ distribution for specific $\ γ$-detection angles and vice versa especially near thresholds for other reaction channels, which shows the potential for significant bias in experiments that, for example, tag on inelastic scattering using a single or small number of $\ γ$ -detection angles and could impact particle transport calculations.

6 ≤ A ≤ 19↗

DOE OSTI2021

Experimental study of the 24 Na m ( d,p ) 25 Na reaction and implications for the influence of the 24 Al m isomer on rp -process nucleosynthesis

A radioactive beam of 24 Na with 90% of its content in its 1 + isomeric state (E ex = 0.472 MeV, t 1/2 = 20.18 ms) has been developed and used to perform a measurement of the 24 Na m ( d,p ) 25 Na reaction at the John D. Fox Accelerator Laboratory at Florida State University. This reaction selectively populated ℓ = 0 transfers, allowing the study of low-spin states in 25 Na. Mirror symmetry arguments were then used to investigate the effects of the isomeric state of 24 Al (E ex = 0.426 MeV, t 1/2 = 130 ms) on the astrophysical rate of the 24 Al m (p,γ) 25 Si reaction. Experimental parameters were extracted to provide, for the first time, an experimental reaction rate for the destruction of 24 Al via proton captures in its isomeric state relevant to rp-process nucleosynthesis.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2020

Charging Reactions Promoted by Geometrically Necessary Dislocations in Battery Materials Revealed by In Situ Single-Particle Synchrotron Measurements

Crystallographic defects exist in many redox active energy materials, e.g., battery and catalyst materials, which significantly alter their chemical properties for energy storage and conversion. However, there is lack of quantitative understanding of the interrelationship between crystallographic defects and redox reactions. Herein, crystallographic defects, such as geometrically necessary dislocations, are reported to influence the redox reactions in battery particles through single-particle, multimodal, and in situ synchrotron measurements. Through Laue X-ray microdiffraction, many crystallographic defects are spatially identified and statistically quantified from a large quantity of diffraction patterns in many layered oxide particles, including geometrically necessary dislocations, tilt boundaries, and mixed defects. The in situ and ex situ measurements, combining microdiffraction and X-ray spectroscopy imaging, reveal that LiCoO 2 particles with a higher concentration of geometrically necessary dislocations provide deeper charging reactions, indicating that dislocations may facilitate redox reactions in layered oxides during initial charging. The present study illustrates that a precise control of crystallographic defects and their distribution can potentially promote and homogenize redox reactions in battery materials.

25 ENERGY STORAGE↗

DOE OSTI2021

New Mechanistic and Reaction Pathway Insights for Oxidative Coupling of Methane (OCM) over Supported Na 2 WO 4 /SiO 2 Catalysts

Abstract The complex structure of the catalytic active phase, and surface‐gas reaction networks have hindered understanding of the oxidative coupling of methane (OCM) reaction mechanism by supported Na 2 WO 4 /SiO 2 catalysts. The present study demonstrates, with the aid of in situ Raman spectroscopy and chemical probe (H 2 ‐TPR, TAP and steady‐state kinetics) experiments, that the long speculated crystalline Na 2 WO 4 active phase is unstable and melts under OCM reaction conditions, partially transforming to thermally stable surface Na‐WO x sites. Kinetic analysis via temporal analysis of products (TAP) and steady‐state OCM reaction studies demonstrate that ( i ) surface Na‐WO x sites are responsible for selectively activating CH 4 to C 2 H x and over‐oxidizing CH y to CO and ( ii ) molten Na 2 WO 4 phase is mainly responsible for over‐oxidation of CH 4 to CO 2 and also assists in oxidative dehydrogenation of C 2 H 6 to C 2 H 4 . These new insights reveal the nature of catalytic active sites and resolve the OCM reaction mechanism over supported Na 2 WO 4 /SiO 2 catalysts.

Sourav, Sagar↗

DOE OSTI2021

New Mechanistic and Reaction Pathway Insights for Oxidative Coupling of Methane (OCM) over Supported Na 2 WO 4 /SiO 2 Catalysts

Sourav, Sagar↗

DOE OSTI2022

Generalized Brønsted‐Evans‐Polanyi Relationships for Reactions on Metal Surfaces from Machine Learning

Abstract Brønsted‐Evans‐Polanyi (BEP) relationships, i. e., a linear scaling between reaction and activation energies, lie at the core of computational design of heterogeneous catalysts. However, BEPs are not general and often require reparameterization for each class of reactions. Here we construct generalized BEPs (gBEPs), which can predict activation energies for a diverse dataset of reactions of C, O, N and H containing molecules on metal surfaces. In a first step we develop a set of descriptors based on scaling relationships that can capture the change in chemical identity of reactants during the reaction. Subsequently, we use the reaction energy, these descriptors and a single descriptor for the surface structure to parameterize machine learning based regression approaches for the prediction of activation energies. The best approach we developed shows a Mean Absolute Error (MAE) of 0.11 eV for the training set (80 % of the data set) and 0.23 eV for the test set (20 % of the data set). The methodology presented here allows to calculate activation energies within fractions of seconds on a typical personal computer and due to its generality, accuracy and simplicity in application it might prove to be useful in transition metal catalyst design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Automated reaction kinetics and network exploration (Arkane): A statistical mechanics, thermodynamics, transition state theory, and master equation software

The open-source statistical mechanics software described here, Arkane–Automated Reaction Kinetics and Network Exploration–facilitates computations of thermodynamic properties of chemical species, high-pressure limit reaction rate coefficients, and pressure-dependent rate coefficient over multi-well molecular potential energy surfaces (PES) including the effects of collisional energy transfer on phenomenological kinetics. Arkane can use estimates to fill in information for molecules or reactions where quantum chemistry information is missing. The software solves the internal energy master equation for complex unimolecular reaction systems. Inputs to the software include converged electronic structure computations performed by the user using a variety of supported software packages (Gaussian, Molpro, Orca, TeraChem, Q-Chem, Psi4). The software outputs high-pressure limit rate coefficients and pressure-dependent phenomenological rate coefficients, as well as computed thermodynamic properties (enthalpy, entropy, and constant pressure heat capacity) with added energy corrections. Some of the key features of Arkane include treatment of 1D, 2D or ND hindered internal rotation modes, treatment of free internal rotation modes, quantum tunneling effect consideration, transition state theory (TST) and Rice-Ramsperger-Kassel-Marcus (RRKM) rate coefficient computations, master equation solution with four implemented methods, inverse-Laplace transform of high-pressure limit rate coefficients into the energy domain, energy corrections based on bond-additivity or isodesmic reactions, automated and efficient PES exploration, and PES sensitivity analysis. The present work describes the design of Arkane, how it should be used, and refers to the theory that it employs. Arkane is distributed via the RMG-Py software suite (https://github.com/ReactionMechanismGenerator/RMG-Py).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Regulatory Coordination of Photophysical, Photochemical, and Biochemical Reactions in the Photosynthesis of Land Plants

Balance among the sequential photophysical, photochemical, and biochemical reactions of photosynthesis is needed for converting fleeting energy in light to stable energy in chemical bonds. Any imbalance acts as either a bottleneck for limiting photosynthetic efficiency or an agent for inducing structural and functional damage to photosynthetic apparatus. Not only must each reaction be carefully regulated, but regulatory processes must also be coordinated across the reactions. However, regulations of different stages of photosynthesis have rarely been studied jointly. Non-photochemical quenching (NPQ) and stomatal conductance (g s ) are key regulators of photophysical and biochemical reactions, respectively. Existing evidence suggests that the redox state of plastoquinone regulates g s and that the photochemical reactions are partially regulated by the ultrastructural dynamics of thylakoids induced by osmotic water fluxes in chloroplasts of land plants. To examine how these regulations are coordinated and feedback to each other, we simultaneously measured NPQ and gs and inferred the redox state of plastoquinone and the light-induced thylakoid swelling/shrinking on numerous C 3 and C 4 species. For all species measured, NPQ and gs covary with the redox states of the electron transport chain, particularly plastoquinone, and increase as thylakoid swelling is inferred. NPQ has the maximal sensitivity at the light intensity at which thylakoid is inferred to be fully swollen. Our findings suggest that plant energy and water use strategies are intimately linked by evolution, and studying the regulations of different photosynthetic stages as a whole can lead to new insights of the functioning of photosynthetic machinery in dynamic environments.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2020

Primary yields of protons measured using CR-39 in laser-induced deuteron–deuteron fusion reactions

The deuteron and deuteron (DD) fusion reactions is the most crucial reaction in the nuclear astrophysics and inertial confinement fusion, which is responsible for synthesizing chemical elements, and for powering the stellar evolution. The plasma environment generated by the high-intensity laser used in a DD fusion reaction is similar to the early stage of the Big Bang. Therefore, it is important to study laser-induced DD fusion reactions. Recently, we experimentally investigated such reactions using eight laser beams with the third harmonic impact on a deuterated polyethylene target at the ShenGuang-II Upgrade facility. In this work, we focused on the application of range-filter spectrometers assembled from a 70 μm aluminum filter and two CR-39 nuclear track detectors to measure the yields of primary DD protons. Based on the track diameter calibration results of 3 MeV protons used to diagnose the tracks on the range- filter spectrometers, we measured a primary DD proton yield of approximately (8:52 ± 1:7) × 10 6 , consistent with the yields from similar laser facilities worldwide, indicating that range-filter spectrometry is an effective way to measure primary DD protons. Furthermore, using other accurate detectors may help to measure the rare events of D 3 He protons.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2022

Reaction chemistry of ethanol oligomerization to distillate-range molecules using low loading Cu/Mg x AlO y catalysts

We study ethanol oligomerization to higher alcohols and other oxygenates with a 0.3 wt. %Cu/Mg 2.9 AlO catalyst. This reaction involves more than 130 products in a complicated reaction network. The selectivity towards diesel fuel precursor compounds (hereafter ‘DFPC’) increased with conversion until reaching a plateau at an ethanol conversion of ~70 %. Alcohol selectivity was found to follow Schultz-Flory distribution at all studied conversions. Larger sized alcohols then are formed mostly by chain-growth mechanisms via surface reactions of adsorbed oligomers with ethanol-based monomers. Higher esters are formed from alcohols and aldehydes in a series reaction mechanism. Moreover, C 6+ ester and C 4+ ketones selectivities increase as conversion increases. We also found that C 4+ alcohols most likely undergo Guerbet coupling with the studied catalyst to form even higher alcohols once, and that the oxygen of these alcohols is active as a nucleophile, resulting in the selective formation of esters if the starting alcohol is branched. Finally, we performed several cofeed studies varying ethanol-to-H 2 inlet partial pressures, and adding acetaldehyde and ethyl acetate as cofeeds to ethanol at different concentrations. Here, we conclude from these experiments that acetaldehyde concentration controls reaction chemistry, with conditions favoring larger concentrations of the molecule promoting both alcohol coupling and ester formation, and conditions leading to lower concentrations of acetaldehyde resulting in higher alcohol selectivity at the expense of esters and higher aldehydes.

10 SYNTHETIC FUELS↗

DOE OSTI2022

An indirect approach to optimize the reaction rates of thermal NO formation for diesel engines

With stringent emission regulations, it has become more important for modern diesel engine manufacturers to accurately predict engine-out nitrogen oxide (NO x ) emissions across a wide range of operating conditions. Thermal NO is the major source of engine-out NO x in modern diesel engines. For thermal NO formation, several earlier studies have recommended the forward and reverse reaction rate coefficients of the rate-limiting reaction (O + N 2 ⇌ NO + N). However, due to deficiencies in sub-models and inadequacies of reduced chemical mechanisms to represent diesel combustion, these recommended values more often than not need to be adjusted in reduced order combustion models to accurately predict engine-out NO x . Hence, in this work a systematic and computationally efficient approach has been proposed to streamline the process of determining the optimum reaction rate coefficients. Here, to develop the optimization approach, four different production diesel engines with different operating conditions in terms of speed, load, and exhaust-gas recirculation have been considered. Numerical simulations have been performed using a detailed zero-dimensional velocity-composition-frequency transported probability density function (0D-VCF-tPDF) model that uses hundreds of notional particles to capture in-cylinder stratification. Four different combinations of hydrocarbon and NO x chemical mechanisms were used to represent chemistry. It was found that for the rate-limiting reaction, the pre-exponent factors (A f1 , A r1 ) and activation energies (E A,f1 , E A,r1 ) of the forward and reverse reaction rates follow a linear band in A f1 - E A,f1 and A r1 - E A,r1 space where predicted engine-out NO x match the measured values closely. By encompassing such bands from different engines and considering constraints on activation energies, a reduced search domain of pre-exponent factors and activation energies was constructed that is expected to be applicable to any diesel engine. Eventually, computationally efficient three-line and one-line search approaches were proposed to determine the optimum values of the pre-exponent factors and activation energies that led to a minimum error between measured and predicted engine-out NO x . Finally, these three-line and one-line NO x optimization approaches were applied to a fifth production diesel engine for which the 0D-VCF-tPDF model showed a very good predictive performance in terms of predicting peak pressure, 50% burn rate, and engine-out NO x when compared to measured and 3D-CFD values.

33 ADVANCED PROPULSION SYSTEMS↗

DOE OSTI2025

Understanding X-ray bursts via direct measurements of ( α , p ) reactions

X-ray bursts, which are thermonuclear explosions on neutron stars accreting mass from companion stars, are the most frequent stellar explosions. To understand the mechanisms behind these bursts, astrophysical models need to incorporate the reaction rates of key nuclear reactions occurring in these stellar environments. This, however, presents significant challenges due to the typically small cross sections of these reactions and the experimental complexities associated with the use of low-intensity radioactive beams. Consequently, most of these reaction rates remain unknown. However, recent advancements in radioactive ion beam facilities and experimental techniques have opened new opportunities to measure these crucial astrophysical reactions. Furthermore, this work explores these advances and highlights recent measurements relevant to X-ray bursts.

Avila, M. L. [Argonne National Laboratory (ANL), A↗

DOE OSTI2020

Characterization of multi-regime reaction zones in a piloted inhomogeneous jet flame with local extinction

In this study, gradient free regime identification (GFRI) is applied to 1D Raman/Rayleigh/LIF measurements of temperature and major species from the intermediate velocity case of the Sydney piloted inhomogeneous jet flame series to better understand the structure of reaction zones and the downstream evolution of multi-regime characteristics. The GFRI approach allows local reaction zones to be detected and characterized as premixed, dominantly premixed, multi-regime, dominantly non-premixed, or non-premixed flame structures, based on flame markers (mixture fraction, chemical mode, and heat release rate) derived from the experimental data. The statistics of chemical mode zero-crossings, which mark premixed reaction zones, and the relative populations of flame structures are shown to be sensitive to the state of mixing in the near field of the flame and to the level of local extinction farther downstream. Multi-regime structures, where premixed and non-premixed reaction zones occur in close proximity and both contribute to overall heat release, account for nearly half the total population at streamwise locations within the first several jet diameters. There is a rapid transition within the near field whereby the relative population of non-premixed and dominantly non-premixed structures grows from 0.05 to nearly 0.5, and the population of premixed and dominantly premixed structures decreases correspondingly as fluid entering the reaction zone becomes progressively fuel-rich. Local extinction and re-ignition bring a resurgence in premixed-type structures, many of which occur at fuel-lean conditions. There are also modest populations of multi-regime structures, having chemical mode zero-crossings at lean conditions, which would not exist in a fully burning jet flame.

42 ENGINEERING↗

DOE OSTI2020

Identification of the molecular-weight growth reaction network in counterflow flames of the C 3 H 4 isomers allene and propyne

The reaction networks responsible for aromatics formation in counterflow flames of the C 3 H 4 isomers allene and propyne are identified through a combined experimental and modeling study. Mole fraction profiles of near-atmospheric pressure (933 mbar) diffusion flames fueled by the C 3 H 4 isomers are analyzed by means of a newly assembled, chemically detailed kinetic mechanism. The experiment consists of a counterflow burner system that is coupled to a high-resolution time-of-flight molecular-beam mass spectrometer with single-photon ionization via synchrotron-generated vacuum-ultraviolet photons. Flame-sampled, mass-specific photoionization efficiency curves are used to identify the presence of aliphatically substituted aromatic species in addition to the commonly considered pericondensed ring structures. The new mechanism describes the formation and growth of aromatics through repetitive sequences of radical–radical and radical–molecule reactions that include C 1 6 intermediates. Higher concentrations of aromatic species are observed in the allene flame and the new mechanism captures the observed experimental trends very accurately. The results indicate the importance of the aliphatically substituted aromatics and of ring-enlargement reactions for the growth reactions. According to the model simulations, radical+radical recombination and PAH-radical+molecule reactions play an important role in PAH growth.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Probing O 2 dependence of hydroperoxy-butyl reactions via isomer-resolved speciation

Degenerate chain-branching mechanisms of n-alkanes are centered on the formation of hydroperoxy-alkyl radicals ($\dot{Q}$OOH), formed via $\dot{R}$ + O 2 reactions, and the ensuing competition between unimolecular decomposition and second-O 2 -addition. Quantitative measurements of partially oxidized intermediates formed via reactions of $\dot{Q}$OOH provide critical constraints that are required for accurate modeling of combustion chemistry. To examine the influence of temperature and oxygen concentration on intermediates from unimolecular decomposition of $\dot{Q}$OOH, isomer-resolved speciation measurements were conducted on n-butane oxidation at 835 Torr in a jet-stirred reactor (JSR) from 500 – 900 K. Resulting from negative-temperature coefficient behavior, cyclic ether formation peaked at two temperatures, 650 K and 800 K, which were selected for separate experiments to quantify the O 2 -dependence of species profiles using O 2 concentrations of 4.2 · 10 17 – 1.1 · 10 19 molecules cm –3 . Utilizing vacuum-ultraviolet absorption spectroscopy and electron-impact mass spectrometry, cyclic ether isomers were quantified separately, including explicit resolution of cis– and trans– isomers of 2,3-dimethyloxirane. Stereoisomers of 2-butene were also quantified explicitly. For all cyclic ethers, a common trend in O 2 -dependence emerged: species concentrations reach a maximum near 3.0 · 10 18 molecules cm –3 (equivalence ratio of 0.5). Although quantitative disparities are evident, chemical kinetics modeling qualitatively reproduces the O 2 dependence of species at 650 K. However, at 800 K, weak dependence on O 2 is predicted, which is in contrast with the measurements. Two carbonyls, diacetyl and methyl vinyl ketone, were also quantified and follow similar dependence on [O 2 ] and temperature as the cyclic ethers, which indicates some fraction forms via $\dot{Q}$OOH-mediated reactions. The discrepancies between the measured and model-predicted species profiles indicate that sub-mechanisms for important intermediates may require additional elementary reactions, including stereochemical-specific reactions, to improve the fidelity of n-alkane combustion modeling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗