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All sources NASA NTRS DOE OSTI

DOE OSTI2022

Automatically generated model for light alkene combustion

Light alkenes are common combustion intermediates for a variety of fuels. Therefore, understanding their oxidation and pyrolysis chemistry is key to building detailed mechanisms for heavier fuels. This work was focused on the development and evaluation of a detailed kinetic mechanism suitable for the combustion of light alkenes up to C 4 without the use of tuned parameters, instead, the parameter values come from first principles or direct measurements. The generated mechanism accurately estimates the laminar burning velocity (S u ) and ignition delay time (IDT) of light alkenes available in the literature, which represent fundamental combustion properties at a wide range of conditions. Because each parameter is thought to have a physically realistic value, not tuned to these measurements, the new model could be used as a sub-mechanism in models for other applications. The reaction network was generated with the open-source Reaction Mechanism Generator (RMG) software. Sensitivity analyses were performed under wide ranges of temperatures and pressures, allowing for the identification of the most impactful species and reactions. Based on these, a comprehensive thermochemistry database, including calculations on 550 molecules performed in this work at the CBS-QB3 level of theory, and a kinetic library, including theoretically-derived reaction rates retrieved from the literature, were built and used in the mechanism generation. The developed mechanism was compared against several existing detailed kinetic mechanisms for ethene, propene, 1-butene, 2-butene, and isobutene. Here, the newly generated model is the most accurate among the ones analyzed, in terms of fractional bias and normalized mean square error. Hence, this new model was used to analyze the chemistry of alkene combustion. Key rate coefficients were compared, to identify the cause of deviations between the models and possible areas for further improvements.

09 BIOMASS FUELS↗

DOE OSTI2022

Combustion chemistry of alkenes and alkadienes

Alkenes formed, during the refining of crude oil, by cracking the heavier fractions are present in transportation fuels in significant amounts, up to as much as 15–20% in gasoline. Moreover, alkenes are also the major intermediate products of the oxidation of alkanes, which play a significant role in autoignition chemistry. This review has assessed the recent progress in gas-phase detailed kinetic model development for species with C=C double bond, mostly C2–C10 alkenes and 1,3-butadiene. The compiled knowledge on alkene combustion chemistry enabled a better understanding of the influence of the number and the position of the C=C double bond on the chemical kinetics and hence combustion behavior of alkenes in engines. At first, the article gives an extensive overview of fundamental combustion experiments by considering studies of C2–C10 alkenes and 1,3-butadiene in shock tubes, rapid compression machines, laminar flames, and jet-stirred and flow reactors. The value of the data from such experiments is critically discussed. Secondly, this article highlights the important reaction classes involved in alkene oxidation over low-, intermediate- and high-temperature ranges. Combustion chemistry covering C2 to C10 alkenes, with a special emphasis on C2 to C7 isomers is discussed by presenting a large body of experimental and modeling investigations. Detailed chemistry differences between alkene isomers and also between alkenes and alkanes are also addressed. Thirdly, the article presents important reaction pathways for PAH precursor formation in different alkenes. Finally, a summary of the distinguishing features of alkene combustion chemistry and an outlook towards future research in this area are presented. In conclusion, this review is focused on linear and branched chain alkenes, and the chemistry of cyclo-alkenes is not included.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Selective Chemical Looping Combustion of Terminal Alkynes in Mixtures with Alkenes

The selective combustion of terminal alkynes in mixtures with alkenes is demonstrated during anaerobic reduction half-cycles on bulk bismuth oxide (Bi 2 O 3 ) as an approach to remove alkynes, which act as inhibitors in olefin polymerization. Bi 2 O 3 combusts phenylacetylene in styrene, 3-methylphenylacetylene in 3-methylstyrene, propyne in propylene, 1-hexyne in 1-hexene, and 1-octyne in 1-octene, with alkyne combustion selectivities exceeding 96%. Near unity reaction orders for hydrocarbon consumption during reduction half-cycles are consistent with combustion pathways initiated by rate-determining initial C–H activation, which drive selective alkyne combustion through intrinsic differences in the first-order rate constants for alkyne and alkene combustion rather than preferential adsorption of alkynes on Bi 2 O 3 surfaces. Computational assessments of initial C–H activation pathways for alkynes and alkenes on (010) α-Bi 2 O 3 surfaces using density functional theory illustrate that heterolytic transition states which form proton-carbanion pairs on Bi–O sites kinetically favor the activation of alkynes rather than alkenes due to differences in C–H bond acidity, and the barrier for heterolytic C–H activation is dictated in part by the sum of the molecular deprotonation energy and the energy to bind an R – carbanion to a Bi site in its transition-state geometry. Finally, these heterolytic reactivity channels during selective chemical looping combustion present novel routes for purifying olefin gas streams containing alkyne impurities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Isomeric effects on the reactivity of branched alkenes: An experimental and kinetic modeling study of methylbutenes

Here, a detailed experimental study of the low-to-intermediate temperature combustion of methylbutene isomers, i.e., branched C 5 alkenes, has been undertaken with multiple experimental facilities. Ignition delay times were measured at equivalence ratios 0.5–2.0, 685–1020 K and up to 45 bar condition from two rapid compression machines and showed slight deviation from an Arrhenius behavior for all three isomers, while their reactivity order differs as temperature changes. Sampled intermediates formed during the oxidation process of mixtures at 900–1150 K and 0.82 bar from a flow reactor and at 730 K and 20 bar from a rapid compression machine were analyzed using gas chromatography techniques. Trends in the formation and consumption of sampled intermediates were modeled using a kinetic model developed in this work for all three isomers. Rate of production and sensitivity analyses emphasize the role of double bond-specific reactions governing the global reactivity of these fuels. Additional studies of the addition reactions of HO 2 radicals to the double bond and to allylic radicals may improve the model performance.

2-Methyl-1-butene↗

DOE OSTI2023

Source Characterization of Volatile Organic Compounds at Carlsbad Caverns National Park

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2023

Source characterization of volatile organic compounds at Carlsbad Caverns National Park

Carlsbad Caverns National Park (CAVE), located in southeastern New Mexico, experiences elevated ground-level ozone (O 3 ) exceeding the National Ambient Air Quality Standard (NAAQS) of 70 ppbv. It is situated adjacent to the Permian Basin, one of the largest oil and gas (O&G) producing regions in the US. In 2019, the Carlsbad Caverns Air Quality Study (CarCavAQS) was conducted to examine impacts of different sources on ozone precursors, including nitrogen oxides (NO x ) and volatile organic compounds (VOCs). Here, we use positive matrix factorization (PMF) analysis of speciated VOCs to characterize VOC sources at CAVE during the study. Seven factors were identified. Three factors composed largely of alkanes and aromatics with different lifetimes were attributed to O&G development and production activities. VOCs in these factors were typical of those emitted by O&G operations. Associated residence time analyses (RTA) indicated their contributions increased in the park during periods of transport from the Permian Basin. These O&G factors were the largest contributor to VOC reactivity with hydroxyl radicals (62%). Two PMF factors were rich in photochemically generated secondary VOCs; one factor contained species with shorter atmospheric lifetimes and one with species with longer lifetimes. RTA of the secondary factors suggested impacts of O&G emissions from regions farther upwind, such as Eagle Ford Shale and Barnett Shale formations. The last two factors were attributed to alkenes likely emitted from vehicles or other combustion sources in the Permian Basin and regional background VOCs, respectively. Implications: Carlsbad Caverns National Park experiences ground-level ozone exceeding the National Ambient Air Quality Standard. Volatile organic compounds are critical precursors to ozone formation. Measurements in the Park identify oil and gas production and development activities as the major contributors to volatile organic compounds. Emissions from the adjacent Permian Basin contributed to increases in primary species that enhanced local ozone formation. Observations of photochemically generated compounds indicate that ozone was also transported from shale formations and basins farther upwind. Therefore, emission reductions of volatile organic compounds from oil and gas activities are important for mitigating elevated O 3 in the region.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

Mechanism, thermochemistry, and kinetics of the reversible reactions: C 2 H 3 + H 2 ⇌ C 2 H 4 + H ⇌ C 2 H 5

High-level coupled cluster theory, in conjunction with Active Thermochemical Tables (ATcT) and E,J-resolved master equation calculations, was used in a study of the title reactions, which play an important role in the combustion of hydrocarbons. In the set of radical/radical reactions leading to soot formation in flames, the addition of H-atoms to alkenes is likely a common reaction, triggering the isomerization of complex hydrocarbons to aromatics. The heats of formation of C 2 H 3 , C 2 H 4 , and C 2 H 5 are established to be 301.26 ± 0.30 at 0 K (297.22 ± 0.30 at 298 K), 60.89 ± 0.11 (52.38 ± 0.11), and 131.38 ± 0.22 (120.63 ± 0.22) kJ mol -1 , respectively. The calculated rate constants from first principles agree well with experiments where they are available. Under conditions typical of high temperature combustion – where experimental work is very challenging with a consequent dearth of accurate data –here we provide high-level theoretical results for kinetic modeling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Bimolecular Peroxy Radical (RO 2 ) Reactions and Their Relevance in Radical Initiated Oxidation of Hydrocarbons

The kinetics of peroxy radical (RO 2 ) reactions have been of long-standing interest in atmospheric and combustion chemistry. Nevertheless, the lack of kinetic studies at higher temperatures for their reactions with other radicals such as OH has precluded the inclusion of this class of reactions in detailed kinetics models developed for combustion applications. In this work, guided by the limited room temperature experimental studies on selected alkyl-peroxy radicals and literature theoretical kinetics on the prototypical CH 3 O 2 + OH system, we have performed parametric studies on the effect of uncertainties in the rate coefficients and branching ratios to potential product channels for RO 2 + OH reactions at higher temperatures. Literature kinetics models were used to simulate autoignition delays, laminar flame speeds, and speciation profiles in flow and stirred reactors for a variety of common combustion-relevant fuels. Inclusion of RO 2 + OH reactions was found to retard autoignition in fuel-lean (φ = 0.5) mixtures of ethane and dimethyl ether in air. The observed effects were noticeably more pronounced in ozone-enriched combustion of ethane and dimethyl ether. The simulations also examined the influence of ozone doping levels, pressures, and equivalence ratios for both ethane and dimethyl ether oxidation. Sensitivity and flux analyses revealed that the RO 2 + OH reaction is a significant sink of RO 2 radicals at the early stage of autoignition, affecting fuel oxidation through RO 2 ↔ QOOH, RO 2 ↔ alkene + HO 2 , or RO 2 + HO 2 ↔ ROOH + O 2 . Additionally, the kinetic stability of the trioxide formed from RO 2 + OH reactions was investigated using master equation analyses. Last, we discuss other bimolecular reactions that are missing in literature kinetics models but are relevant to hydrocarbon oxidation initiated by external radical sources (plasma-enhanced, ozone-enriched combustion, etc.). In conclusion, the present simulations provide a strong motivation for better characterizing the bimolecular kinetics of peroxy radicals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Theoretical analysis of QOOH combustion reaction pathways

QOOH radicals are key intermediates in the chain of reactions leading to the autoignition of hydrocarbons and oxygenated organic compounds. They are thought to undergo two main reactions: OH elimination to form a cyclic ether and HO2 elimination to form an alkene. However, theoretical analysis of various substituted hydroperoxyalkyl radicals has found two new pathways: OH transfer and internal H abstraction assisted OH elimination. To determine the importance of these new pathways, their barrier heights for several substituted alkanes were calculated using various quantum chemical theories and compared to those of the well-known pathways. Several cases revealed possible competition with the well-known pathways. Rate coefficients were calculated for propyl systems but further studies will need to complete rate coefficients and branching fractions for all systems analyzed to understand these new reactions’ role in autoignition.

33 ADVANCED PROPULSION SYSTEMS↗

NASA NTRS1980

Fuels characterization studies

Current analytical techniques used in the characterization of broadened properties fuels are briefly described. Included are liquid chromatography, gas chromatography, and nuclear magnetic resonance spectroscopy. High performance liquid chromatographic ground-type methods development is being approached from several directions, including aromatic fraction standards development and the elimination of standards through removal or partial removal of the alkene and aromatic fractions or through the use of whole fuel refractive index values. More sensitive methods for alkene determinations using an ultraviolet-visible detector are also being pursued. Some of the more successful gas chromatographic physical property determinations for petroleum derived fuels are the distillation curve (simulated distillation), heat of combustion, hydrogen content, API gravity, viscosity, flash point, and (to a lesser extent) freezing point.

Seng, G. T.↗

NASA NTRS2019

Emissions Relationships in Western Forest Fire Plumes: I. Reducing the Effect of Mixing Errors on Emission Factors

Studies of emission factors from biomass burning using aircraft data complement the results of lab studies and extend them to conditions of immense hot conflagrations. We illustrate and discuss emission relationships for 422 individual samples from many forest-fire plumes in the Western US. The samples are from two NASA investigations: ARCTAS (Arctic Research of the Composition of the Troposphere from Aircraft and Satellites) and SEAC4RS (Studies of Emissions and Atmospheric Composition, Clouds, and Climate Coupling by Regional Surveys). This work provides sample-by-sample enhancement ratios (EnRs) for 23 gases and particulate properties. Many EnRs provide candidates for emission ratios (ERs, corresponding to the EnR at the source) when the origin and degree of transformation is understood and appropriate. From these, emission factors (EFs) can be estimated when the fuel dry mass consumed is known or can be estimated using the carbon mass budget approach. This analysis requires understanding the interplay of mixing of the plume with surrounding air. Some initial examples emphasize that measured C(tot) = CO2 + CO in a fire plume does not necessarily describe the emissions of the total carbon liberated in the flames, C(burn). Rather, it represents C(tot) = C(burn) + C(bkgd), which includes possibly varying background concentrations for entrained air. Consequently, we present a simple theoretical description for plume entrainment for multiple tracers from flame to hundreds of kilometers downwind and illustrate some intrinsic linear behaviors. The analysis suggests a Mixed Effects Regression Emission Technique (MERET), which can eliminate occasional strong biases associated with the commonly used normalized excess mixing ratio (NEMR) method. MERET splits C(tot) to reveal C(burn) by exploiting the fact that C(burn) and all tracers respond linearly to dilution, while each tracer has consistent EnR behavior (slope of tracer concentration with respect to C(burn)). The two effects are separable. Two or three or preferably more emission indicators are required as a minimum; here we used ten. Limited variations in the EnRs for each tracer can be incorporated and the variations and co-variations analyzed. The percentage CO yield (or the modified combustion efficiency) plays some role. Other co-relationships involving nitrogen and organic classes are more prominent; these have strong relationships to the C(burn) to O3 emission relationship. In summary, MERET allows fine spatial resolution (EnRs for individual observations) and comparison of similar plumes distant in time and space. Alkene ratios provide us with an approximate photochemical timescale. This allows discrimination and definition, by fire situation, of ERs, allowing us to estimate emission factors.

Chatfield, Robert B.↗

DOE OSTI2024

Tracking the reaction networks of acetaldehyde oxide and glyoxal oxide Criegee intermediates in the ozone-assisted oxidation reaction of crotonaldehyde

The reaction of unsaturated compounds with ozone (O 3 ) is recognized to lead to the formation of Criegee intermediates (CIs), which play a key role in controlling the atmospheric budget of hydroxyl radicals and secondary organic aerosols. The reaction network of two CIs with different functionality, i.e. acetaldehyde oxide (CH 3 CHOO) and glyoxal oxide (CHOCHOO) formed in the ozone-assisted oxidation reaction of crotanaldehyde (CA), is investigated over a temperature range between 390 K and 840 K in an atmospheric pressure jet-stirred reactor (JSR) at a residence time of 1.3 s, stoichiometry of 0.5 with a mixture of 1% crotonaldehyde, 10% O 2 , at an fixed ozone concentration of 1000 ppm and 89% Ar dilution. Molecular-beam mass spectrometry in conjunction with single photon tunable synchrotron vacuum-ultraviolet (VUV) radiation is used to identify elusive intermediates by means of experimental photoionization energy scans and ab initio threshold energy calculations for isomer identification. Addition of ozone (1000 ppm) is observed to trigger the oxidation of CA already at 390 K, which is below the temperature where the oxidation reaction of CA was observed in the absence of ozone. The observed CA + O 3 product, C 4 H 6 O 4 , is found to be linked to a ketohydroperoxide (2-hydroperoxy-3-oxobutanal) resulting from the isomerization of the primary ozonide. Products corresponding to the CIs uni- and bi-molecular reactions were observed and identified. A network of CI reactions is identified in the temperature region below 600 K, characterized by CIs bimolecular reactions with species like aldehydes, i.e., formaldehyde, acetaldehyde, and crotonaldehyde and alkenes, i.e., ethene and propene. The region below 600 K is also characterized by the formation of important amounts of typical low-temperature oxidation products, such as hydrogen peroxide (H 2 O 2 ), methyl hydroperoxide (CH 3 OOH), and ethyl hydroperoxide (C 2 H 5 OOH). Detection of additional oxygenated species such as alcohols, ketene, and aldehydes are indicative of multiple active oxidation routes. This study provides important information about the initial step involved in the CIs assisted oligomerization reactions in complex reactive environments where CIs with different functionalities are reacting simultaneously. It provides new mechanistic insights into ozone-assisted oxidation reactions of unsaturated aldehydes, which is critical for the development of improved atmospheric and combustion kinetics models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2005

Identification and Quantitative Measurements of Chemical Species by Mass Spectrometry

The development of a miniature gas chromatograph/mass spectrometer system for the measurement of chemical species of interest to combustion is described. The completed system is a fully-contained, automated instrument consisting of a sampling inlet, a small-scale gas chromatograph, a miniature, quadrupole mass spectrometer, vacuum pumps, and software. A pair of computer-driven valves controls the gas sampling and introduction to the chromatographic column. The column has a stainless steel exterior and a silica interior, and contains an adsorbent of that is used to separate organic species. The detection system is based on a quadrupole mass spectrometer consisting of a micropole array, electrometer, and a computer interface. The vacuum system has two miniature pumps to maintain the low pressure needed for the mass spectrometer. A laptop computer uses custom software to control the entire system and collect the data. In a laboratory demonstration, the system separated calibration mixtures containing 1000 ppm of alkanes and alkenes.

Zondlo, Mark A.↗

DOE OSTI2026

Directed Gas-Phase Formation of The Propargyl Family of Resonance-Stabilized Radicals in The Reactions of Ground-State Carbon Atoms (C; 3 P j ) with Butene Isomers (C 4 H 8 ): Dimethylpropargyl and Ethylpropargyl

The propargyl radical (C 3 H 3 ) is the simplest resonance-stabilized free radical (RSFR), but how does stepwise methyl substitution in the alkene reactant affect its dynamics of their formation? We report a crossed molecular beam study of the reactions of atomic carbon (C, 3 P j ) with four butene isomers (C 4 H 8 ) under single collision conditions at a collision energy of 28 ± 2 kJ mol −1 . Barrierless addition of atomic carbon to the alkene C=C bond triggers ring opening to triplet substituted allenes—a de facto insertion mechanism—followed by unimolecular decomposition via atomic hydrogen (H), methyl (CH 3 ) or ethyl (C 2 H 5 ) loss, yielding a family of propargyl‑type RSFRs. RRKM calculations reveal that the branching ratios are highly sensitive to the alkene structure. While the methyl loss channel, affording 1‑methylpropargyl, dominates for 2 butenes (80–90%), the predicted hydrogen atom loss channel (≈10%) leading to 1,3 dimethylpropargyl is identified in the experiment by comparison with theoretical energetics. For isobutene, a near‑equal competition is seen, with the reaction producing 3‑methylpropargyl (≈50%) and 1,1‑dimethylpropargyl (≈40%), along with 2‑vinylallyl (≈5%), whose formation is supported by the experimental data. Most notably, the reaction with 1 butene uniquely favors an enthalpically driven hydrogen shift, eventually producing 1 vinylallyl (≈38%), which is assigned based on the excellent agreement between the measured and calculated reaction exothermicity. Rapid entropically favored fragmentation channels yield ≈40% of propargyl type species (propargyl, 1- and 3-ethylpropargyls), slightly outcompeting the allyl type product. Furthermore, these results establish a systematic progression from C 2 H 4 to C 4 H 8 , where the increasing alkyl substitution unlocks new fragmentation channels, providing a versatile gas phase route to alkylated RSFRs—key intermediates in the growth of methylated and ethylated PAHs and aliphatic chains in combustion and cold interstellar environments (molecular clouds).

Alkyls↗

DOE OSTI2022

Machine Learning Models for Binary Molecular Classification using VUV Absorption Spectra

Machine learning methods were combined with differential absorption spectroscopy measurements in the vacuum-ultraviolet region (5.167 – 9.920 eV) in order to develop predictive capabilities for inferring molecular structure from the spectra. Several types of species were analyzed and, for modeling purposes, were defined using a single classification: (1) alkane, (2) conjugation with oxygen (e.g. diacetyl, ethyl vinyl ether), (3) non-conjugated alkene (e.g. 1-butene, 1,4-cyclohexadiene), (4) oxygen-containing (e.g. 1-butanol, tetrahydrofuran), or (5) cyclic (e.g. cyclopentane, cyclohexanone). The latter molecular classification excluded cyclic ethers. Several modeling methods were employed in the analysis of 102 absorption spectra, 24 of which were measured for the first time. The primary objective was to identify suitable methods that enable accurate predictions of molecular structure classifications with minimized statistical uncertainties. Rather than identifying a single, unifying method to reliably predict molecular structure contributions to VUV absorption spectra, coordination is required among a particular method, the type of molecular structure detail (e.g. conjugation), and absorption region of interest. The latter is accomplished using a binning approach, wherein absorption regions of ~0.5 eV were utilized rather than the entire ~4.8 eV range. Photon energy binning enabled analysis of region-specific predictions of accuracy, precision, and recall. The outcome from the binning approach is that, rather than utilizing the entire spectrum, optimal determination of molecular structure using machine learning methods depends on the absorption region. Furthermore, the present work provides separate machine learning models for each molecular classification, which enables the identification of multi-functional species relevant to atmospheric chemistry and combustion chemistry, where isomer-resolved speciation is critical to understanding complex reaction networks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗