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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 1,657 records · Page 92
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Diesel Fuel Property Effects on In-Cylinder Liquid Penetration Length: Impact on Smoke Emissions and Equivalence Ratio Estimates at the Flame Lift-Off Length

Here in this study, elastic scattering was employed to investigate diesel fuel property effects on the liquid length (i.e., the maximum extent of in-cylinder liquid-phase fuel penetration) using select research fuels: an ultralow-sulfur #2 diesel emissions-certification fuel (CF) and four of the Coordinating Research Council (CRC) Fuels for Advanced Combustion Engines (FACE) diesel fuels (F1, F2, F6, and F8). The experiments were performed in a single-cylinder heavy-duty optical compression-ignition engine under time-varying, noncombusting conditions to minimize the influence of chemical heat release on the liquid-length measurement. The FACE diesel fuel and CF liquid lengths under combusting conditions were also predicted using Siebers’ scaling law and pressure data from previous work using the same fuels at similar in-cylinder conditions. The objective was to observe if the liquid length under noncombusting or combusting conditions provides additional insights into the relationships among the main fuel properties (i.e., cetane number (CN), the 90 vol % distillation recovery temperature (T90), and aromatic content) and smoke emissions. Results suggest that liquid-length values are best correlated to fuel distillation characteristics measured with ASTM D2887 (simulated distillation method). This work also studied the relationship between liquid length and lift-off length, H (i.e., distance from the fuel-injector orifice exit to the position where the standing premixed autoignition zone stabilizes during mixing-controlled combustion). Two possible cases were identified based on the relative magnitudes of liquid length under combusting conditions (Lc) and H. The low-CN fuels are representative of the first case, L c < H, in which the fuel is always fully vaporized at H. The high-CN fuels are mostly representative of the second case, L c ≥ H, in which there is still liquid fuel at H. Lc ≥ H would suggest higher smoke emissions, but there is not enough evidence in this work to support a compounding effect of a longer liquid length on top of the aromatic-content effect on smoke emissions for fuels with similar CN, supporting previous findings in the literature that lift-off length plays a more important role than liquid-length on diesel combustion. At the same time, the experimental results suggest a decrease in the fuel-jet spreading angle, i.e., a decrease in the entrainment rate into the jet at and downstream of H, under combusting conditions, that is not accounted for in the model used to predict the values of $\phi$(H). Lastly, as a result, L c may be of interest for accurate predictions of $\phi$(H), especially for combustion strategies designed to lower in-cylinder soot by operating near or below the nonsooting $\phi$(H)-value (i.e., $\phi$(H) ≈ 2).

02 PETROLEUM↗
DOE OSTI2018

Detailed Experimental and Kinetic Modeling Study of Cyclopentadiene Pyrolysis in the Presence of Ethene

A combined experimental and kinetic modeling study is presented to improve the understanding of the formation of polycyclic aromatic hydrocarbons at pyrolysis conditions. The copyrolysis of cyclopentadiene (CPD) and ethene was studied in a continuous flow tubular reactor at a pressure of 0.17 MPa and a dilution of 1 mol CPD/1 mol ethene/10 mol N 2 . The temperature was varied from 873 to 1163 K, resulting in cyclopentadiene conversions between 1 and 92%. Using an automated reaction network generator, RMG, we present an elementary step kinetic model for CPD pyrolysis that accurately predicts the initial formation of aromatic products. The model is able to reproduce the product yields measured during the pyrolysis of pure cyclopentadiene and the copyrolysis of cyclopentadiene and ethene. The addition of ethene as coreactant increases the benzene and toluene selectivity. In the absence of ethene, benzene formation is initiated by addition of a cyclopentadienyl radical to cyclopentadiene, following a complicated series of isomerizations and loss of a butadienyl radical. In the presence of ethene, the main pathway for the formation of benzene + CH 3 shifts to ethene + cyclopentadiene. Toluene formation is initiated by vinyl radical addition to cyclopentadiene. Without the addition of ethene, vinyl radicals are mainly formed by hydrogen radical addition to ethyne. As a result, when ethene is added as coreactant, vinyl radical production happens via hydrogen abstraction from ethene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Effect of Microwave and Thermal Co-pyrolysis of Low-Rank Coal and Pine Wood on Product Distributions and Char Structure

Direct conversion of a low-rank coal into valuable chemicals or improving its char’s coking value became very demanding aims in coal utilization strategies. Here, the co-pyrolysis of a low-rank lignite coal and pine wood sawdust biomass blended at a 3:1 coal-to-biomass ratio was investigated along with original coal and biomass samples by microwave-assisted and conventional thermal methods at 550 °C under nitrogen and ambient pressure. The carbon structure and its reactivity in generated chars and the product distributions were greatly affected by the applied heating mechanism and the presence of biomass during coal pyrolysis. High gas and low tar yields were observed for all microwave chars in comparison to thermal chars, regardless of composition. The addition of biomass to coal increased the tar yield under both methods and to a higher extent under the microwave. This agrees with the high gas yield and high aromatic-to-aliphatic fraction observed under the microwave and the presence of biomass. The high O/C ratio and low fixed carbon content in a biomass structure relative to coal affect the product distribution during microwave pyrolysis. This could selectively heat the biomass in the sample, remove its polar groups, and convert it into an efficient microwave absorber biochar that can decompose coal efficiently during co-pyrolysis. The aromatic carbon stacking and its ordering in the generated chars were investigated by powder X-ray diffraction, Raman spectroscopy, dielectric property measurements, and electron spin resonance techniques. A synergistic effect was observed upon biomass addition during microwave coal pyrolysis. Electron spin resonance spectroscopy revealed that the microwave coal/biomass char is the most stable char with the lowest free radical concentration. Furthermore, this agrees with the highest I G /I all band area ratio calculated from Raman analysis revealing a more graphitic nature for carbon in this char. Similarly, the dielectric properties confirmed that the addition of biomass to coal under the microwave has the highest loss tangent, indicating a high graphitic nature compared to pure biochar or coal char.

09 BIOMASS FUELS↗
DOE OSTI2021

Root carbon interation with soil minerals is dynamic, leaving a legacy of microbially derived residues

Minerals preserve the oldest most persistent soil carbon, and mineral characteristics appear to play a critical role in the formation of soil organic matter (SOM) associations. To test the hypothesis that carbon source and soil microorganisms also influence mineral-SOM associations, we incubated permeable minerals bags in soil microcosms with and without plants, in a 13CO2 labelling chamber. Mineral bags contained quartz, ferrihydrite, kaolinite, or native soil minerals isolated via density separation. Using 13C-NMR, FTICR-MS, and lipidomics, we traced plant-derived carbon onto minerals harvested from microcosms at three plant growth stages, characterizing total carbon, 13C enrichment, and SOM chemistry. While C accumulation was rapid and mineral-dependent, the accumulated amount was not significantly affected by the presence of plant roots. However, the rhizosphere did shape the chemistry of mineral-associated SOM. Minerals incubated in the rhizosphere were associated with a more diverse array of compounds with different C functional groups (carbonyl, aromatics, carbohydrates, lipids) than minerals incubated in a bulk soil control. These diverse rhizosphere-derived compounds may represent a “transient fraction” of mineral SOM, rapidly exchanging with mineral surfaces. Our results also suggest that many of the lipids which persist on minerals are microbially-derived with a large fraction of fungal lipids.

Rhizosphere, soil organic matter, grassland, 13C-N↗
DOE OSTI2022

Molecular Characterization of Water-Soluble Brown Carbon Chromophores in Snowpack from Northern Xinjiang, China

This study reports molecular-level characterization of brown carbon (BrC) attributed to water-soluble organic carbon in six snowpack samples collected from northern Xinjiang, China. Here, the molecular composition and light-absorbing properties of BrC chromophores were unraveled by application of high-performance liquid chromatography (HPLC) coupled to a photodiode array (PDA) detector and high-resolution mass spectrometry. The chromophores were classified into five major types, that is, (1) phenolic/lignin-derived compounds, (2) flavonoids, (3) nitroaromatics, (4) oxygenated aromatics, and (5) other chromophores. Identified chromophores account for ~23–64% of the total light absorption measured by the PDA detector in the wavelength range of 300–370 nm. In the representative samples from urban and remote areas, oxygenated aromatics and nitroaromatics dominate the absorption in the wavelengths below and above 320 nm, respectively. The highly polluted urban sample shows the most complex HPLC-PDA chromatogram, and more other chromophores contribute to the bulk absorption. Phenolic/ lignin-derived compounds are the most light-absorbing species in the soil-influenced sample. Chromophores in two remote samples exhibit ultraviolet–visible features distinct from other samples, which are attributed to flavonoids. Identification of individual chromophores and quantitative analysis of their optical properties are helpful for elucidating the roles of BrC in snow radiative balance and photochemistry.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2015

Abiotic Bromination of Soil Organic Matter

Biogeochemical transformations of plant-derived soil organic matter (SOM) involve complex abiotic and microbially mediated reactions. One such reaction is halogenation, which occurs naturally in the soil environment and has been associated with enzymatic activity of decomposer organisms. Building on a recent finding that naturally produced organobromine is ubiquitous in SOM, we hypothesized that inorganic bromide could be subject to abiotic oxidations resulting in bromination of SOM. Through lab-based degradation treatments of plant material and soil humus, we have shown that abiotic bromination of particulate organic matter occurs in the presence of a range of inorganic oxidants, including hydrogen peroxide and assorted forms of ferric iron, producing both aliphatic and aromatic forms of organobromine. Bromination of oak and pine litter is limited primarily by bromide concentration. Fresh plant material is more susceptible to bromination than decayed litter and soil humus, due to a labile pool of mainly aliphatic compounds that break down during early stages of SOM formation. As the first evidence of abiotic bromination of particulate SOM, this study identifies a mechanistic source of the natural organobromine in humic substances and the soil organic horizon. Formation of organobromine through oxidative treatments of plant material also provides insights into the relative stability of aromatic and aliphatic components of SOM.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

Molecular Characterization of Brown Carbon in Biomass Burning Aerosol Particles

Emissions from biomass burning are a significant source of brown carbon (BrC) in the atmosphere. In this study, we investigate the molecular composition of freshly-emitted biomass burning organic aerosol (BBOA) samples collected during test burns of selected biomass fuels: sawgrass, peat, ponderosa pine, and black spruce. We characterize individual BrC chromophores present in these samples using high performance liquid chromatography coupled to a photodiode array detector and a high-resolution mass spectrometer. We demonstrate that both the overall BrC absorption and the chemical composition of light-absorbing compounds depend significantly on the type of biomass fuels and burning conditions. Common BrC chromophores in the selected BBOA samples include nitro-aromatics, polycyclic aromatic hydrocarbon derivatives, and polyphenols spanning a wide range of molecular weights, structures, and light absorption properties. A number of biofuel-specific BrC chromophores are observed, indicating that some of them may be used as potential markers of BrC originating from different biomass burning sources. On average, ~50% of the light absorption above 300 nm can be attributed to a limited number of strong BrC chromophores, which may serve as representative light-absorbing species for studying atmospheric processing of BrC aerosol. The absorption coefficients of BBOA are affected by solar photolysis. Specifically, under typical atmospheric conditions, the 300 nm absorbance decays with a half-life of 16 hours. A “molecular corridors” analysis of the BBOA volatility distribution suggests that many BrC compounds in the fresh BBOA have low volatility (<1 g m-1) and will be retained in the particle phase under atmospherically relevant conditions.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2017

Interconnection of Key Microbial Functional Genes for Enhanced Benzo[ a ]pyrene Biodegradation in Sediments by Microbial Electrochemistry

Sediment microbial fuel cells (SMFCs) can stimulate the degradation of polycyclic aromatic hydrocarbons in sediments, but the mechanism of this process is poorly understood at the microbial functional gene level. Here, the use of SMFC resulted in 92% benzo[ a ]pyrene (B a P) removal over 970 days relative to 54% in the controls. Sediment functions, microbial community structure, and network interactions were dramatically altered by the SMFC employment. Functional gene analysis showed that c -type cytochrome genes for electron transfer, aromatic degradation genes, and extracellular ligninolytic enzymes involved in lignin degradation were significantly enriched in bulk sediments during SMFC operation. Correspondingly, chemical analysis of the system showed that these genetic changes resulted in increases in the levels of easily oxidizable organic carbon and humic acids which may have resulted in increased B a P bioavailability and increased degradation rates. In conclusion, tracking microbial functional genes and corresponding organic matter responses should aid mechanistic understanding of B a P enhanced biodegradation by microbial electrochemistry and development of sustainable bioremediation strategies.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2018

Stability of Ferrihydrite–Humic Acid Coprecipitates under Iron-Reducing Conditions

Recent studies have suggested the potential for release of iron (hydr)oxide-bound organic carbon (OC) during dissimilatory iron oxide reduction (DIR). However, the stability of iron (hydr)oxide-bound OC in the presence of a natural microbial consortium capable of driving both OC metabolism and DIR has not been resolved. Pure ferrihydrite (Fhy) and Fhy-humic acid coprecipitates (Fhy-HA) were inoculated with a small quantity of freshwater sediment and incubated under anoxic conditions in the presence and absence of H 2 or glucose as electron donors for DIR. H 2 promoted DIR led to release of ca. 1 mM dissolved organic carbon (DOC). However, comparable amounts of DOC were released from both pure Fhy and Fhy-HA, similar to DOC levels in mineral-free, inoculum-only controls. These results suggest that the observed DOC release during H 2 -promoted DIR originated from OC contained in the inoculum as opposed to the much larger pool (ca. 38 mM) of OC in the Fhy-HA. Thus, DIR preferentially released sorbed OC with low aromaticity (inoculum OC) versus highly aromatic OC (HA) coprecipitated with iron oxide. Furthermore, our findings provide new insight into the extent and mechanisms by which DIR is likely to influence aqueous/solid-phase OC partitioning in anoxic soils and sediments.

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

Study of the Hydrogen Pretreatment of Gallium and Platinum Promoted ZSM-5 for the Ethane Dehydroaromatization Reaction

Here, the performances of gallium and platinum promoted ZSM-5 catalysts, fresh and reduced, were studied for the dehydroaromatization of ethane to aromatics. Fresh and reduced 2% Ga/ZSM-5, 1.5% Ga–0.5% Pt/ZSM-5, and 0.5% Pt/ZSM-5 were tested in a fixed-bed reactor system at 615 °C for 2 h time on stream. It was observed that the hydrogen reduction of the fresh Pt-containing catalysts led to an increase in catalytic conversion. The addition of platinum to the gallium catalyst resulted in an increase in the reducibility of the Ga species on the surface of the zeolite. The GaPt catalysts exhibited an increase in ethane conversion and the stability of aromatic production selectivity over the Ga and Pt catalysts. The as-prepared fresh catalysts were characterized by ICP and BET methods. The fresh and reduced catalysts were further analyzed by XRD, H 2 -TPR, XPS, pyridine DRIFTS, TGA, and TEM.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Fabrication of a Pillared ZSM-5 Framework for Shape Selectivity of Ethane Dehydroaromatization

Ethane, the second major component of shale gas, is a prospective raw feedstock to valuable chemicals and fuels. Innovative pillared ZSM-5 with various lamellar thicknesses and Si/Al ratios were successfully synthesized with the dual-template method; 0.67 wt % Mo were dispersed over these lamellar ZSM-5, and evaluated for ethane dehydroaromatization. The influence of zeolite morphology and the texture property for the reduction/acidity nature of MoOx species were investigated by X-ray diffraction, scanning electron microscopy, N2-sorption, H2-temperature programmed reduction/oxidation, and NH3-temperature-programmed desorption. The high concentration of acidic sites not only increases ethane conversion and aromatic selectivity, but intensely induces surface coking. Therefore, a moderate Si/Al ratio is utilized to balance catalytic reactivity and stability. Thicker zeolite layers with a long diffusion path exhibited fair ethane conversion, but high aromatization yield. It is of significant importance that the lamellar Mo/MFI catalyst, with Si/Al = 50 and 210 nm layer thickness, demonstrated excellent regenerability during a multicycle reaction/oxidation operation, which could be a promising system for industrial optimization and process deployment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Integrated Two-Stage Alkaline-Oxidative Pretreatment of Hybrid Poplar. Part 1: Impact of Alkaline Pre-Extraction Conditions on Process Performance and Lignin Properties

We previously demonstrated that a two-stage pretreatment comprising of an alkaline pre-extraction followed by a Cu-catalyzed alkaline–oxidative treatment is effective at pretreating hardwoods under relatively mild reaction conditions. In this work, we focus on characterizing how biomass source and reaction conditions used during the alkaline pre-extraction impact the subsequent processing stages as well as lignin yields and properties. Specifically, three hybrid poplars were subjected to the first stage alkaline pre-extraction under various conditions including differences in time (15–300 min), temperature (95–155 °C), and alkali loadings (50–200 mg NaOH/g biomass), and the impact on total mass solubilization, lignin recovery, and lignin purity was determined. Empirical correlations were developed between reaction conditions and mass solubilization and lignin recovery during the pre-extraction stage. For select conditions, lignin properties were assessed and include β-O-4 content determined by 13C NMR, molecular mass distributions as determined by gel permeation chromatography, and susceptibility to depolymerization to aromatic monomers using thioacidolysis and formic acid catalyzed depolymerization. We found alkaline pre-extraction performed at higher temperatures generated lignins exhibiting lower contamination by polysaccharides, lower aromatic monomer yields from depolymerization, lower molar masses, and lower β-O-4 contents relative to the lower temperature pre-extractions. Lastly, the pre-extracted biomass from select conditions was assessed for its response to the subsequent Cu-catalyzed alkaline–oxidative treatment and enzymatic hydrolysis. It was demonstrated that minor differences in delignification during pre-extraction have quantifiable impacts on the subsequent efficacy of the second stage of pretreatment and enzymatic hydrolysis with improved lignin removal during the first pre-extraction stage resulting in improved hydrolysis yields.

09 BIOMASS FUELS↗
DOE OSTI2019

110th Anniversary: Microkinetic Modeling of the Vapor Phase Upgrading of Biomass-Derived Oxygenates

Bio-oil produced from fast pyrolysis of biomass is a complex mixture of more than 200 compounds, including oxygenates and acids. As these species are highly undesirable in fuels, catalytic upgrading of biomass pyrolysis product vapors, also known as catalytic fast pyrolysis, is performed to upgrade the vapors to valuable fuels and chemicals. This work presents a detailed microkinetic model, composed of elementary steps, of the catalytic upgrading of acetic acid and acetone, two common oxygenates present in bio-oil. An automated network generator was utilized to construct a reaction network composed of 580 unique species and 2160 unique reactions. The kinetic parameters for each reaction in the network were estimated using transition state theory, the Evans-Polanyi relationship, and thermodynamic data. The resulting mechanistic model is able to describe experimental data presented in the literature for the transformation of acetic acid and acetone on HZSM-5 in a fixed-bed reactor, which is modeled as a plug-flow reactor. Additionally, the model solutions reveal vital information regarding the mechanism by which acetic acid and acetone are upgraded to valuable fuels and chemicals. In the first phase of the mechanism, acetic acid is converted to acetone via acylium ion addition to acetic acid; this is followed by decarboxylation of acetoacetic acid. The second phase is dominated by the self-aldol condensation of acetone, which is shown to occur predominantly through the keto form of acetone rather than the enol form, and subsequent deoxygenation reactions leading to olefins and aromatics. Finally, net rate analysis shows that aromatics are primarily formed via a pathway including aldol condensation of mesityl oxide, whereas olefins are produced from the addition of isobutene and subsequent cracking.

09 BIOMASS FUELS↗
DOE OSTI2020

Structural Features of Zirconium-Based Metal–Organic Frameworks Affecting Radiolytic Stability

Metal–organic frameworks (MOFs) NU-1000 and UiO-66 are herein exposed to two different gamma irradiation doses and dose rates and analyzed to determine the structural features that affect their stability in these environments. MOFs have shown promise for the capture and sensing of off-gases at civilian nuclear energy reprocessing sites, nuclear waste repositories, and nuclear accident locations. However, little is understood about the structural features of MOFs that contribute to their stability levels under the ionizing radiation conditions present at such sites. This study is the first of its kind to explore the structural features of MOFs that contribute to their radiolytic stability. Both NU-1000 and UiO-66 are MOFs that contain Zr metal-centers with the same metal absorption cross section. However, the two MOFs exhibit different linker connectivities, linker aromaticities, node densities, node connectivities, and interligand separations. In this study, NU-1000 and UiO-66 were exposed to high (423.3 Gy/min, 23 min, and 37 s) and low (0.78 Gy/min, 4320 min) dose rates of 60 Co gamma irradiation. NU-1000 displayed insignificant radiation damage under both dose rates due to its high linker connectivity, low node density, and low node connectivity. However, low radiation dose rates caused considerable damage to UiO-66, a framework with lower aromaticity and smaller interligand separation. Finally, results suggest that chronic, low-radiation environments are more detrimental to Zr MOF stability than acute, high-radiation conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Reactive Molecular Dynamics Simulations and Quantum Chemistry Calculations To Investigate Soot-Relevant Reaction Pathways for Hexylamine Isomers

Sooting tendencies of a series of nitrogen-containing hydrocarbons (NHCs) have been recently characterized experimentally using the yield sooting index (YSI) methodology. This work aims to identify soot-relevant reaction pathways for three selected C6H15N amines, namely, dipropylamine (DPA), diisopropylamine (DIPA), and 3,3-dimethylbutylamine (DMBA) using ReaxFF molecular dynamics (MD) simulations and quantum mechanical (QM) calculations and to interpret the experimentally observed trends. ReaxFF MD simulations are performed to determine the important intermediate species and radicals involved in the fuel decomposition and soot formation processes. QM calculations are employed to extensively search for chemical reactions involving these species and radicals based on the ReaxFF MD results and also to quantitatively characterize the potential energy surfaces. Specifically, ReaxFF simulations are carried out in the NVT ensemble at 1400, 1600, and 1800 K, where soot has been identified to form in the YSI experiment. These simulations account for the interactions among test fuel molecules and pre-existing radicals and intermediate species generated from rich methane combustion, using a recently proposed simulation framework. ReaxFF simulations predict that the reactivity of the amines decrease in the order DIPA > DPA > DMBA, independent of temperature. Both QM calculations and ReaxFF simulations predict that C2H4, C3H6, and C4H8 are the main nonaromatic soot precursors formed during the decomposition of DPA, DIPA, and DMBA, respectively, and the associated reaction pathways are identified for each amine. Both theoretical methods predict that sooting tendency increases in the order DPA, DIPA, and DMBA, consistent with the experimentally measured trend in YSI. This work demonstrates that sooting tendencies and soot-relevant reaction pathways of fuels with unknown chemical kinetics can be identified efficiently through combined ReaxFF and QM simulations. Overall, predictions from ReaxFF simulations and QM calculations are consistent, in terms of fuel reactivity, major intermediates, and major nonaromatic soot precursors.

fuel decomposition↗
DOE OSTI2020

Application of Self-Interaction Corrected Density Functional Theory to Early, Middle, and Late Transition States

Density functional theory (DFT)-based methods often significantly underpredict chemical reaction barriers compared with experiments because of the tendency of DFT to over-stabilize transition states with stretched bonds due to the impact of unphysical electron self-interaction. But many reactions have early or late transition states where the transition state geometry closely resembles the reactants or products, respectively. The role of self-interaction in those cases is not known. Here we compare the performance of DFT with and without self-interaction correction (SIC) for describing the hydrogenation of CO and CO 2 catalyzed by a Lewis acid-base pair incorporated onto an aromatic cluster, using CCSD(T) results for reference. The three elementary steps in these reactions consist of an early, a middle, and a late transition. Our results show that the Perdew-Zunger SIC (PZ-SIC), implemented in the Fermi-L Lowdin orbital SIC (FLO-SIC) approach, qualitatively improves the description of the forward and reverse reaction barriers relative to uncorrected DFT for the middle transition, but not the early or late transitions. By contrast, the local scaling SIC (LSIC) method, also implemented in the FLO-SIC framework, significantly improves the calculated barriers over DFT and PZ-SIC in all but one case. Lastly, the results also show how the FLO-SIC approach can provide insight into the bonding in aromatic systems.

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

Radical–Radical Reactions in Molecular Weight Growth: The Phenyl + Propargyl Reaction

The mechanism for hydrocarbon ring growth in sooting environments is still the subject of considerable debate. The reaction of phenyl radical (C 6 H 5 ) with propargyl radical (H 2 CCCH) provides an important prototype for radical–radical ring-growth pathways. We studied this reaction experimentally over the temperature range of 300–1000 K and pressure range of 4–10 Torr using time-resolved multiplexed photoionization mass spectrometry. We detect both the C 9 H 8 and C 9 H 7 + H product channels and report experimental isomer-resolved product branching fractions for the C 9 H 8 product. We compare these experiments to theoretical kinetics predictions from a recently published study augmented by new calculations. Here, these ab initio transition state theory-based master equation calculations employ high-quality potential energy surfaces, conventional transition state theory for the tight transition states, and direct CASPT2-based variable reaction coordinate transition state theory (VRC-TST) for the barrierless channels. At 300 K only the direct adducts from radical–radical addition are observed, with good agreement between experimental and theoretical branching fractions, supporting the VRC-TST calculations of the barrierless entrance channel. As the temperature is increased to 1000 K we observe two additional isomers, including indene, a two-ring polycyclic aromatic hydrocarbon, and a small amount of bimolecular products C 9 H 7 + H. Our calculated branching fractions for the phenyl + propargyl reaction predict significantly less indene than observed experimentally. We present further calculations and experimental evidence that the most likely cause of this discrepancy is the contribution of H atom reactions, both H + indenyl (C 9 H 7 ) recombination to indene and H-assisted isomerization that converts less stable C 9 H 8 isomers into indene. Especially at low pressures typical of laboratory investigations, H-atom-assisted isomerization needs to be considered. Regardless, the experimental observation of indene demonstrates that the title reaction leads, either directly or indirectly, to the formation of the second ring in polycyclic aromatic hydrocarbons.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Critical Assessment of Photoionization Efficiency Measurements for Characterization of Soot-Precursor Species

We present a critical evaluation of photoionization efficiency (PIE) measurements coupled with aerosol mass spectrometry for the identification of condensed soot-precursor species extracted from a premixed atmospheric-pressure ethylene/oxygen/nitrogen flame. Definitive identification of isomers by any means is complicated by the large number of potential isomers at masses likely to comprise particles at flame temperatures. This problem is compounded using PIE measurements by the similarity in ionization energies and PIE-curve shapes among many of these isomers. Nevertheless, PIE analysis can provide important chemical information. For example, our PIE curves show that neither pyrene nor fluoranthene alone can describe the signal from C 16 H 10 isomers and that coronene alone cannot describe the PIE signal from C 24 H 12 species. A linear combination of the reference PIE curves for pyrene and fluoranthene yields good agreement with flame-PIE curves measured at 202 u, which is consistent with pyrene and fluoranthene being the two major C 16 H 10 isomers in the flame samples, but does not provide definite proof. The suggested ratio between fluoranthene and pyrene depends on the sampling conditions. We calculated the values of the adiabatic-ionization energy (AIE) of 24 C 16 H 10 isomers. Despite the small number of isomers considered, the calculations show that the differences in AIEs between several of the isomers can be smaller than the average thermal energy at room temperature. The calculations also show that PIE analysis can sometimes be used to separate hydrocarbon species into those that contain mainly aromatic rings and those that contain significant aliphatic content for species sizes investigated in this study. Our calculations suggest an inverse relationship between AIE and the number of aromatic rings. We have demonstrated that further characterization of precursors can be facilitated by measurements that test species volatility.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗