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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 433 records · Page 24
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Autoignition of CRC diesel surrogates at low temperature combustion conditions: Rapid compression machine experiments and modeling

As federal programs require increasingly stringent engine emissions and fuel economy standards, these ambitions can only be met if next-generation combustion technology is developed focusing on high-efficiency and low-emissions engines. Recent research has indicated the need to operate engines at higher compression ratios and with low temperature combustion (LTC) to achieve the needed gains in engine efficiency and reductions in emissions. Because there is a lack of understanding of the chemistry of diesel fuel components and their mixtures at these LTC conditions, this limits the ability to develop predictive chemical kinetic models that can be used to optimize engine combustion. The current study aims to fill in gaps in fundamental combustion data on surrogate fuel mixtures relevant to diesel fuels. Specifically, four multicomponent diesel surrogates formulated by the Coordinating Research Council (CRC) to emulate an ultra-low-sulfur research-grade #2 certification diesel fuel (CFA), namely V0a (4 components), V0b (5 components), V1 (8 components), and V2 (9 components), have been investigated in a rapid compression machine (RCM) through determination of total and first-stage ignition delay times. Autoignition characteristics of lean to rich fuel/O 2 /N 2 mixtures, for the four CRC surrogates and CFA, have been measured using an RCM at LTC relevant pressures and temperatures, in the ranges of 10–20 bar and 650–1000 K, respectively. The equivalence ratios have been varied by independently changing the oxygen mole fraction and the fuel mole fraction in the test mixtures, thereby illustrating the individual effects of oxygen concentration and fuel loading on diesel autoignition. Autoignition results of these four CRC surrogates are compared among them and with those of CFA. Some degree of agreement in autoignition response between each CRC surrogate and CFA is observed, while discrepancies are also identified and discussed. In addition, a detailed chemical kinetic model for diesel surrogates has been developed and validated against these newly-acquired RCM data. We find that this model shows reasonable agreement with the overall ignition delay time results of the current RCM experiments. Chemical kinetic analyses of the developed model were further conducted to help identify the reactions controlling the autoignition processes and the consumption of fuel components in CRC surrogates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Availability and reactivity of N 2 ( v ) for NH 3 synthesis by plasma catalysis

Production of vibrationally excited N 2 (N 2 (v)) in atmospheric pressure nonthermal plasma and loss of N 2 (v) by gas-phase reactions and reactions on catalytic surfaces are analyzed to examine the role of N 2 (v) in NH 3 formation by plasma catalysis. Vibrational state-to-state kinetic models complemented with molecular beam mass spectrometry (MBMS) measurements demonstrate that N 2 (v> 0) is produced with densities 100× greater than the density of N radicals by a radiofrequency atmospheric pressure plasma jet. The experimentally measured loss of N 2 (v) corresponds with a state-to-state kinetic model that describes loss of N 2 (v) by surface-mediated vibrational relaxation without consideration of reactions that convert N 2 (v) to NH 3 over the catalyst surface. Rate constants for vibrational relaxation of N 2 (v) on catalyst surfaces exceed upper bounds on proposed rate constants for NH 3 formation reactions from N 2 (v) over Fe when v < 9, Ni when v < 18, and Ag when v < 39, which indicates that only higher vibrational levels can possibly contribute to catalytic NH 3 formation faster than they undergo vibrational relaxation on the surface. Densities of N 2 (v> 8), vibrational levels that can possibly react over Fe to form NH 3 faster than they undergo vibrational relaxation, are less than or similar to N densities at the inlet of the catalyst bed and measured NH 3 formation for the investigated conditions in this work, while densities of N 2 (v> 17) and N 2 (v> 38) are orders of magnitude below the N density at the inlet of the catalyst bed and the measured NH 3 formation. The loss of N 2 (v) by vibrational relaxation on the surface limits the ability of N 2 (v) to contribute to catalytic NH 3 formation and explains why N 2 (v) does not produce NH 3 in quantities that are comparable to NH 3 formation from N even though N 2 (v > 0) is more abundantly produced by the plasma.

state-to-state kinetic modeling↗
NASA NTRS2018

Tuning Process for the Modified Magnussen Combustion Model

In the application of CFD to turbulent reacting flows, one of the main limitations to predictive accuracy is the chemistry model. Using a full or skeletal kinetics model may provide good predictive ability, however, at considerable computational cost. Adding the ability to account for the interaction between turbulence and chemistry improves the overall fidelity of a simulation but adds to this cost. An alternative is the use of simple models, such as the Magnussen model, which has negligible computational overhead, but lacks general predictive ability except for cases that can be tuned to the flow being solved. In this paper, a technique will be described that allows the tuning of the Magnussen model for an arbitrary fuel and flow geometry without the need to have experimental data for a particular case. The tuning is based on comparing the results of the Magnussen model and full finite-rate chemistry when applied to perfectly and partially stirred reactor sim- ulations. In addition, a modification to the Magnussen model is proposed that allows the upper kinetic limit for the reaction rate to be set, giving better physical agreement with full kinetic mechanisms. In order to improve the agreement with flame temperatures, the thermal properties of the product species is adjusted to better match the mixture proper- ties of the full mechanism. The combustion model is then applied to the simulation of a representative scramjet flowpath, and the results compared to experimental data and other kinetic models. This procedure allows a simple reacting model to be used in a predictive manner, and affords significant savings in computational costs for CFD simulations.

Norris, A. T.↗
NASA NTRS2019

Considerations for Femtosecond Laser Electronic Excitation Tagging in High-Speed Flows

Femtosecond laser electronic excitation tagging (FLEET) is an unseeded method for molecular tagging which offers valuable opportunities for measurement of high-speed (transonic, supersonic or hypersonic) flows. The unique nature of high-speed testing demands certain performance from FLEET such as satisfactory signal-to-noise ratio (SNR) at depressed static conditions (i.e., low temperatures, pressures and densities), wide dynamic range for velocity determination (especially single-shot), and measurements with acceptable accuracy and precision. This dissertation strives to evaluate FLEET in those regards and provide strategies to maximize the method's capabilities. A zero-dimensional kinetics model in nitrogen explains FLEET signal changes with pressure/density and/or temperature in terms of plasma-chemical reactions. Poorly known rate coefficients are tuned by comparing model output to measurements, with temporal agreement up to several hundred nanoseconds. Modeling reveals that initial signal peaks at reduced density because of slowed temporal evolution (and decay) of excited populations. Low temperatures enhance signal by enlarging cluster ion populations which contribute to excited species via electron-ion dissociative recombination. A purpose-built free jet facility provides experimental validation of the kinetics model and assesses FLEET velocimetry in low temperature and pressure/density conditions. Signal, lifetime, accuracy and precision results are obtained from unheated subsonic through Mach 4.0 operation of the facility, with best results noted. FLEET measurements of a sweeping jet (SWJ) actuator in compressible operation showcase its advantages in a highly unsteady jet containing subsonic through supersonic velocities. FLEET velocimetry is performed in the device's internal and external flow fields, with the latter compared to hot-wire anemometry. Internal measurements reveal the absence of shockwaves theorized to occur at high pressure ratios. Simultaneous qualitative measurements of compressible jet mixing are shown as a proof-of-concept. Overall, the work demonstrates that previous understanding of SWJ incompressible operation readily extends into the compressible realm. Practical aspects of performing FLEET velocimetry are detailed, along with strategies for improving measurement quality. Determination of a fundamental precision in nitrogen and air is attempted. Experiments show that increasing time delay and/or SNR improves velocimetry precision. A comparison of five camera systems indicates sensors with larger pixels capture higher SNR data and produce more precise results.

FLEET↗
DOE OSTI2022

Time-resolved measurements of HO 2 radical in a heated plasma flow reactor

Time-resolved, absolute HO 2 number density in diluted H 2 –O 2 –Ar, CH 4 –O 2 -Ar, and C 2 H 4 –O 2 –Ar mixtures excited by a repetitive ns pulse discharge in a heated plasma flow reactor is measured by Cavity Ringdown Spectroscopy (CRDS). The experimental results are obtained at $\textit{T}$ = 300-600 K and $\textit{P}$ = 130 Torr, both during the discharge pulse burst and in the afterglow. In this work, the HO 2 number density is inferred from the CRDS data using a spectral model exhibiting good agreement with previous measurements of absolute HO 2 absorption cross sections. In the room-temperature H 2 –O 2 mixture, as well as in CH 4 –O 2 and C 2 H 4 –O 2 mixtures over the entire temperature range studied, HO2 is generated only during the discharge burst and decays in the afterglow. However, in the H 2 –O 2 mixture at elevated temperatures, $\textit{T}$ = 400-600 K, HO 2 persists in the afterglow up to 10 ms after the discharge burst, comparable with the flow residence time in the reactor. Comparison with kinetic modeling shows that the sustained reactivity after the source of radicals is turned off is due to a chain propagation / hydrogen oxidation process, which dominates the radical recombination reactions. The kinetic modeling predictions are in good agreement with the relative HO 2 number density measured in all three mixtures, although the model underpredicts the absolute number densities in H 2 –O 2 at $\textit{T}$ = 400-600 K by up to a factor of two. Detection of the sustained low-temperature reactivity in H 2 –O 2 , initiated by the radical generation in the plasma, suggests that the plasma excitation may also affect kinetics of oxidation and reforming of fuels exhibiting low-temperature chemistry below hot ignition point.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2019

Wholly Heterocycles-Based Polyamide–Sulfide Containing Pyridine and Thiazole Rings: A Super-Adsorbent Polymer for Lead Removal

Wholly heterocycles-based polyamide-sulfide (PAS) containing pyridine and thiazole rings with thioether linkage was synthesized and used as a novel adsorbent for lead ion removal from water. The polymer adsorbent was fully characterized via FTIR, NMR and scanning electron microscopy (SEM). The thermal properties of the synthesized polyamide were also studied by thermogravimetric analysis and the outcome showed that the polymer has a good to moderate thermal stability. The SEM was used to investigate the morphology of the wholly heterocycles-based polyamide and the outcomes displayed a porous and globular-like morphology, which guarantee effective metal adsorption. Pb(II) ion removal capacity of the synthesized polymer was studied by varying the contact time and the adsorbent concentration. The maximum removal of Pb(II) was obtained as 99%. Equilibrium behavior and kinetic of the adsorption were also investigated using prevalent isotherm and kinetic models. The adsorption capacity was obtained to be around 714 mg g{sup −1}. The Langmuir isotherm and the pseudo-second order kinetic model suggested superior agreement with the equilibrium and kinetic adsorption data, respectively. Generally, the results of this research demonstrated that the synthesized polymer is a super-adsorbent for heavy metal removal from water.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Non-isothermal Crystallization and Degradation Kinetics of Fe{sub 3}O{sub 4}–Thymolblue Functionalized Poly(ε-caprolactone)

The Fe{sub 3}O{sub 4}–thymolblue (TB) functionalized or end capped poly(ε-caprolactone) (PCL) was synthesized by ring opening polymerization (ROP) of ε-caprolactone (CL) with Fe{sub 3}O{sub 4}–TB nanohybrid as an effective initiator in the presence of stannous octoate (SO) as a catalyst. The main aim of the present work is to analyze the influence of polymer chain end capping agent or functionalization agent on the structure–property relationship particularly, crystallization and thermal degradation behavior of PCL under non-isothermal condition. The structure of the polymer was analyzed using FTIR and NMR spectra. The particle size of the incorporated Fe{sub 3}O{sub 4}–TB nanohybrid in PCL matrix was found to be less than 20 nm by TEM. The surface morphology, skewness moment and surface roughness were analysed by AFM. The spherulitic growth of the nucleated polymer crystals was confirmed by POM. The spherulitic growth was further verified with various kinetic models. The melting and crystallization behaviors under non-isothermal condition were assessed by DSC. Various kinetic models were employed to comprehend the degradation behavior of Fe{sub 3}O{sub 4}–TB functionalized PCL and its associated kinetic parameters under non-isothermal condition. The energy of activation (E{sub a}) for the crystallization and thermal degradation of PCL were found to be 132 and nearly 140 kJ/mol respectively.

36 MATERIALS SCIENCE↗
NASA NTRS1989

Kinetic theory model for the flow of a simple gas from a two-dimensional nozzle

A system of nonlinear integral equations equivalent to the Krook kinetic equation for the steady state is the mathematical basis used to develop a computer code to model the flowfields for low-thrust two-dimensional nozzles. The method of characteristics was used to solve numerically by an iteration process the approximated Boltzmann equation for the number density, temperature, and velocity profiles of a simple gas as it exhausts into a vacuum. Results predict backscatter and show the effect of the inside wall boundary layer on the flowfields external to the nozzle.

Riley, B. R.↗
NASA NTRS1991

Kinetic theory model for the flow of a simple gas from a three-dimensional axisymmetric nozzle

A system of nonlinear integral equations equivalent to the Krook kinetic equations for the steady state is the mathematical basis used to develop a computer code to model the flowfields for low-thrust three-dimensional axisymmetric nozzles. The method of characteristics is used to solve numerically by an iteration process the approximated Boltzmann equation for the number density, temperature, and velocity profiles of a simple gas as it expands into a vacuum. Results predict backscatter and show the effect of the nozzle wall boundary layer on the external flowfields.

Riley, B. R.↗
DOE OSTI2023

Laminar flame speed measurements of a gasoline surrogate and its mixtures with ethanol at elevated pressure and temperature

Laminar Flame speed measurements of a gasoline surrogate and mixtures of it with ethanol were conducted using a heated, constant-volume vessel. A spherical propagating flame was observed using a high-speed camera, and laminar flame speed was determined therefrom. Here, the gasoline surrogate, which serves as the baseline for the current study, consisted of four components, namely, iso-octane, n-heptane, toluene, and 1-hexene. Different mixtures of the gasoline surrogate and ethanol were studied, governed by the ethanol percentage in the mixture. That is, E0, E30, E50, and E85 mixtures represent 0%, 30%, 50%, and 85% ethanol in the gasoline surrogate mixture by liquid volume, respectively. Initial temperatures of 335, 359, and 408 K and initial pressures of 1 and 3 bar were investigated. The findings of this study are compared to results in the literature, which show good agreement for E0 but some deviation for the E30 blend. In general, the study showed an increase in laminar flame speed as the ethanol percentage increases in the mixture. Similarly, increasing the initial temperature with fixed ethanol percentage resulted in an increase in laminar flame speed, as expected. In contrast, increasing the initial pressure with fixed Ethanol percentage showed a decrease in laminar flame speed. Finally, the results are compared to an existing chemical kinetics model designed for ethanol and gasoline. Although agreement between the model and data is reasonable and mostly within about 10%, some improvement to the kinetics model is needed to uniformly lower the calculated flame speeds.

09 BIOMASS FUELS↗
DOE OSTI2024

Can Third-Body Stabilization of Bimolecular Collision Complexes in Cold Molecular Clouds Happen?

For more than half a century, networks of radiative association, dissociative recombination, and bimolecular reactions have been postulated to drive the low-temperature chemistry of cold molecular clouds. Third-body stabilizations of collision complexes have been assumed to be 'irrelevant' due to short lifetime of such complexes. Here, we conduct crossed molecular beam studies of ground state atomic silicon with diacetylene in combination with electronic structure calculations and microcanonical kinetics models operating under cold molecular cloud conditions. Our combined experimental, electronic structure, and microcanonical kinetics modelling investigations provide compelling evidence that three-body collisions of molecular hydrogen with long-lived reaction intermediates accessed through intersystem crossing are prevalent deep inside molecular clouds. This concept might be exportable to reactions involving polycyclic aromatic hydrocarbons thus affording a versatile machinery to complex organics via third-body stabilizations of bimolecular collision complexes deep inside cold molecular clouds.

astrochemistry↗
DOE OSTI2020

Towards a UV model of kinetic mixing and portal matter

The nature of dark matter (DM) and how it might interact with the particles of the Standard Model (SM) is an ever-growing mystery. It is possible that the existence of new “dark sector” forces, yet undiscovered, are the key to solving this fundamental problem, and one might hope that in the future such forces might even be “unified” with the ones we already know in some UV-complete framework. In this paper, following a bottom-up approach, we attempt to take the first steps in the construction of such a framework. The much-discussed possibility of the kinetic mixing (KM) of the “dark photon” with the hypercharge gauge boson of the SM via loops of portal matter (PM) fields, charged in both sectors, offers an attractive starting point for these efforts. Given the anticipated finite strength of the KM in a UV-complete theory, the absence of anomalies, and the lifetime constraints on the PM fields arising from cosmic microwave background and nucleosynthesis constraints, PM must behave as vector-like copies of the known SM fermion fields, such as those which appear naturally in, e.g., E 6 -type models. Within such a setup, the SM and their corresponding partner PM fields would be related by a new S U ( 2 ) I gauge symmetry. With this observation as a springboard, we construct a generalization of these ideas where S U ( 2 ) I is augmented by an additional U ( 1 ) I Y factor so that the light dark photon is the result of a symmetry breaking analogous to the SM, i.e., S U ( 2 ) I × U ( 1 ) I Y → U ( 1 ) D , but with U ( 1 ) D now also broken at the ≲ GeV scale. While SM fields are U ( 1 ) D singlets, as in the conventional dark photon approach, they transform nontrivially under the full S U ( 2 ) I × U ( 1 ) I Y gauge group. This approach leads to numerous interesting signatures, both at low energies and at colliders, and can be viewed as an initial step in the construction of a more UV-complete framework.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2025

A neural master equation framework for multiscale modeling of molecular processes: application to atomic-scale plasma processes

Plasma-surface interactions (PSI) play a crucial role in microelectronics fabrication; however, their multiscale nature and array of complex, often unknown interactions make computational modeling of PSIs extremely difficult. To this end, we propose a general neural master equation (NME) framework that uses master equations to describe the dynamics of a molecular process, wherein neural networks learned from atomistic simulations represent unknown transitions between different system states. By leveraging the physics-based structure of master equations and data-driven state transitions, the NME framework promotes generalizability and physics interpretability, and can bridge disparate length and time scales. The framework is demonstrated for multiscale modeling of Si atomic layer etching and reactive ion etching, where the learned NME-based surface kinetic models exhibit good predictive and extrapolative capabilities for predicting experimentally relevant observables as a function of process parameters. The NME-based surface kinetic models obey physical constraints, which are violated in models based on neural ordinary differential equations. The proposed NME framework for multiscale modeling of molecular processes can pave the way for the discovery of new chemistries and materials in atomic-scale plasma processes.

Chemical engineering↗
DOE OSTI2024

Toward UV models of kinetic mixing and portal matter. V. Indirect probes of the new physics scale

Kinetic mixing of the dark photon, the gauge boson of a hidden U ( 1 ) D , with the Standard Model (SM) gauge fields to induce an interaction between ordinary matter and dark matter (DM) at 1-loop requires the existence of portal matter (PM) fields having both dark and SM charges. As discussed in earlier work, these same PM fields can also lead to other loop-level mechanisms besides kinetic mixing that can generate significant interactions between SM fermions and the dark photon in a manner analogous to those that can be generated between a Dirac neutrino and a SM photon, i.e., dark moments. In either case, there are reasons to believe, e.g., due to the renormalization group equation running of the U ( 1 ) D gauge coupling, that PM fields may have ∼ TeV -scale masses that lie at or above those directly accessible to the HL-LHC. If they lie above the reach of the HL-LHC, then the only way to possibly explore the physics at this high scale in the short term is via indirect measurements made at lower energies, e.g., at lepton colliders operating in the m Z to 1 TeV range. In particular, processes such as e + e − → γ + DM or e + e − → f ¯ f , where f is a SM fermion, may be most useful in this regard. Here we explore these possibilities within the framework of a simple toy PM model, introduced in earlier work, based on a non-Abelian dark gauge group completion operating at the PM scale. In the kinetic mixing setup, we show these efforts fail due to the inherently tiny cross sections in the face of substantial SM backgrounds. However, in the case of interactions via induced dark moments, since they necessarily take the form of higher dimensional operators whose influence grows with energy, we show that access to PM-scale information may become possible for certain ranges of the toy model parameters for both of these e + e − processes at a 1 TeV collider. Published by the American Physical Society 2024

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
NASA NTRS1993

Dispersed ion structures at the poleward edge of the auroral oval: Low-altitude observations and numerical modeling

We have compared the AUREOL 3 (A3) observations of auroral ion precipitation, particularly ion beams, with the results from the global kinetic model of magnetotail plasma of Ashour-Abdalla et al. (1993). We have identified 101 energetic keV H(+) velocity dispersed precipitating ion structures (VDIS) with fluxes above 10(exp -3) ergs./sq cm./s in the A3 record between the end of 1981 and mid-1984. These beams display a systematic increase in energy with increasing latitude and were observed in a narrow region within less than 1 deg in latitude of the polar cap boundary. The VDIS are the most distinctive feature in the auroral zone of the plasma sheet boundary layer. We report first on a statistical analysis of the possible ralationships between magnetic activity or substorm phase and the VDIS properties. Our particle simulations of the precipitating ions have been extended by using a series of modified versions of the Tsyganenko (1989) magnetic field model and by varying the cross-magnetosphere electric field. In the simulations, plasma from a mantle source is subject to strong nonlinear acceleration, forming beams which flow along the PSBL. Only 3 to 4% of these beams precipitate into the ionosphere to form the VDIS while the majority return to the equatorial plane after mirroring and form the thermalized central plasma sheet. The final energy and the dispersion of the beams in the model depend on the amplitude of the cross-tail electric field. Two unsual observations of low-energy (less than 5 keV) O(+) VDIS, shifted by 4 deg 5 deg in invariant latitude equatorward of H(+) VDIS are analyzed in detail. The sparsity of such O(+) events and the absence of the changes in the flux and frequency of occurrence indicate a solar wind origin for the plasma. Finally, large-scale kinetic modeling, even with its simplifications and assumptions (e.g., static magnetic field, solar wind source), reproduces low-altitude auroral ion features fairly well; it may therefore be presented as an appropriate framework into which data on energization and transport of the hot plasma, obtained in the equatorial plane, could be inserted in the near future.

Bosqued, J. M.↗
DOE OSTI2024

Rotating cylinder electrode in reactive CO 2 capture: Identifying active C species via transport, VLE models and kinetics

Here, this article explores technical challenges and potential methodologies for understanding electrochemical Reactive CO 2 Capture (RCC) mechanisms. RCC offers potential energy cost advantages by directly converting captured CO 2 into fuels and chemicals, unlike traditional carbon capture and utilization (CCU) processes that require sequential capture, concentration, and compression. However, direct conversion of captured CO 2 introduces complexity due to additional equilibrium buffer reactions, making it challenging to identify active species for reduction in electrochemical studies. This article discusses methods to integrate transport, thermodynamics, and kinetics concepts to identify active carbon sources in RCC. Vapor‐Liquid Equilibrium (VLE) and transport models are validated against experimental results obtained in a gastight rotating cylinder electrode reactor and are shown as useful tools for studying RCC in heterogeneous electrocatalysts across different capture agents, solvents, and temperatures. This article establishes an experimental framework for advancing research in electrochemical RCC.

Electrocatalysis↗
DOE OSTI2020

Cool flame chemistry of diesel surrogate compounds: n -Decane, 2-methylnonane, 2,7-dimethyloctane, and n -butylcyclohexane

Elucidating the formation of combustion intermediates is crucial to validate reaction pathways, develop reaction mechanisms and examine kinetic modeling predictions. While high-temperature pyrolysis and oxidation intermediates of alkanes have been thoroughly studied, comprehensive analysis of cool flame intermediates from alkane autoxidation is lacking and challenging due to the complexity of intermediate species produced. Here, jet-stirred reactor autoxidation of four C 10 alkanes: n -decane, 2-methylnonane, 2,7-dimethyloctane, and n -butylcyclohexane, as model compounds of diesel fuel, was investigated from 500 to 630 K using synchrotron vacuum ultraviolet photoionization molecular beam mass spectrometry (SVUV-PIMS). Around 100 intermediates were detected for each fuel. The classes of molecular structures present during the autoxidation of the representative paraffinic functional groups in transport fuels, i.e., n -alkanes, branched alkanes, and cycloalkanes were established and were found to be similar from the oxidation of various alkanes. A theoretical approach was applied to estimate the photoionization cross sections of the intermediates with the same carbon skeleton as the reactants, e.g., alkene, alkenyl keto, cyclic ether, dione, keto-hydroperoxide, diketo-hydroperoxide, and keto-dihydroperoxide. These species are indicators of the first, second, and third O 2 addition reactions for the four C 10 hydrocarbons, as well as bimolecular reactions involving keto-hydroperoxides. Chemical kinetic models for the oxidation of these four fuels were examined by comparison against mole fraction of the reactants and final products obtained in additional experiments using gas chromatography analysis, as well as the detailed species pool and mole fractions of aforementioned seven types of intermediates measured by SVUV-PIMS. This works reveals that the models in the literature need to be improved, not only the prediction of the fuel reactivity and final products, but also the reaction network to predict the formation of many previous undetected intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗