Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “kinetic mechanisms”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
NASA NTRS2024

Fundamental Experimental Tests and Modeling of LOX/CH4 Engines at High Pressures

In recent years, the space travel industry has grown exponentially, resulting in the need for a low-cost, efficient rocket engine fuel. As such, there has been renewed interest in utilizing liquid natural gas (LNG) as it is less likely to soot than kerosene-based fuels and has widespread availability and low cost of use as compared to the traditional RP-X and even liquid methane (LCH4) fuels due to the reduced need for refinement. However, current literature does not fully cover varying blends of natural gas and the effects that impurities have on natural gas/methane fuels, with most studies being confined to low-pressure applications. Therefore, new experimental ignition delay time measurements at rocket engine relevant pressures are essential to ensure current chemical kinetic models capture the ignition behavior at these elevated conditions and to determine the optimal purity levels for a reliable, cost-efficient, aerospace-grade LCH4/LNG fuel. The current work explores various blends of natural gas/methane fuel with various impurities, including higher hydrocarbons as well as nitrogen-carriers. A shock tube study was carried out to study the ignition delay times and carbon monoxide time histories of these natural gas blends utilizing chemiluminescence and laser absorption spectroscopy at 20, 50 and 100 atm over temperatures ranging from 1400-1700K and at an equivalence ratio of 1. The experimental data was then compared to two different chemical kinetic mechanisms: the industry-standard GRI 3.0 and the in-house UCF 2022. The data is used to improve chemical kinetic mechanisms and modeling of LNG fuels for rocket engine applications.

Methane↗
NASA NTRS1983

Kinetics and mechanism of the oxidation of S(IV) by ozone in aqueous solution with particular reference to SO2 conversion in nonurban tropospheric clouds

Results are presented from a laboratory study of the kinetics of the S(IV)-O3 reaction in aqueous solution, including measurements of the effects of UV radiation, dissolved transition metals, and an antioxidant (hydroquinone) on the rate. On the basis of the results, relative rates of S(IV) conversion by O3 in tropospheric cloud water are compared with those predicted for H2O2 and for O2. The reaction mechanism is discussed, with an outline given of the elements of a possible reaction scheme. Application of the rate constants obtained to SO2 conversion in cloud water predicts conversion rates by ozone to be competitive with those by H2O2 at pH above about 4.5 and to dominate at pH above about 5.5. It is pointed out that since these pH's are typical for nonurban tropospheric cloud water, ozone is a potentially important contributor to the overall oxidative conversion of SO2 to sulfate in the nonurban troposphere.

Maahs, H. G.↗
DOE OSTI2024

Mechanism-Guided Kinetic Analysis of Electrocatalytic Proton Reduction Mediated by a Cobalt Catalyst Bearing a Pendant Basic Site

Cobalt polypyridyl complexes stand out as efficient catalysts for electrochemical proton reduction, but investigations into their operating mechanisms, with broad-reaching implications in catalyst design, have been limited. Herein, we investigate the catalytic activity of a cobalt(II) polypyridyl complex bearing a pendant pyridyl base with a series of organic acids spanning 20 pKa units in acetonitrile. Structural analysis, as well as electrochemical studies, reveals that the Co(III) hydride intermediate is formed through reduction of the Co(II) catalyst followed by direct metal protonation in the initial EC step despite the presence of the pendant base, which is commonly thought of as a more kinetically accessible protonation site. Protonation of the pendant base occurs after the Co(III) hydride intermediate is further reduced in the overall ECEC pathway. Additionally, when the acid used is sufficiently strong, the Co(II) catalyst can be protonated, and the Co(III) hydride can react directly with acid to release H 2 . With thorough mechanistic understanding, the appropriate electroanalytical methods were identified to extract rate constants for the elementary steps over a range of conditions. Thermodynamic square schemes relating catalytic intermediates proposed in the three electrocatalytic HER mechanisms were constructed. Furthermore, these findings reveal a full description of the HER electrocatalysis mediated by this molecular system and provide insights into strategies to improve synthetic fuel-forming catalysts operative through metal hydride intermediates.

08 HYDROGEN↗
NASA NTRS1987

Hydrogen oxidation mechanism with applications to (1) the chaperon efficiency of carbon dioxide and (2) vitiated air testing

Ignition delay times for the hydrogen/oxygen/carbon dioxide/argon system were obtained behind reflected shock waves. A detailed kinetic mechanism modeled the experimental hydrogen/oxygen data, Skinner and Ringrose's high-pressure data, and Slack and Grillo's hydrogen/air data. A carbon dioxide chaperon efficiency of 7.0 +/- 0.2 was determined. The reaction pathway H2O yields H2O2 yields OH yields H was required to model the high-pressure data. It is suggested that some of the lowest temperature data points (1.0 and 0.5 atm) for Slack and Grillo's hydrogen/air experiments are in error. It was found that the technique of simplifying a detailed kinetic mechanism for a limited range of experimental data may render the model useless for other test conditions.

Brabbs, Theodore A.↗
DOE OSTI2026

Early-stage uranium-hydrogen corrosion kinetics and mechanism

Research into the early-stage uranium-hydrogen degradation mechanism lacks unified interpretation and understanding due to inadequate temporal and spatial characterization resolution required to unify reaction observations. In this study, white-light interferometry was adapted to characterize the uranium-hydrogen reaction at a temperature of 50 °C and hydrogen pressure of 13.8 kPa. The uranium surface remained unchanged for 62 min during the hydride induction period before the first hydride blister appeared. This blister was monitored from induction through critical spallation and UH₃ powder release during rapid surface hydriding. The critical spallation dimensions measured for height, diameter, area, and perimeter of the first blister were 1.79 µm, 17.58 µm, 187.7 µm 2 and 59.79 µm. Hydriding growth kinetics were assessed by tracking the first hydride site over the reaction time. Analysis shows that the spall-front velocity of the hydride was changing at a rate of 0.91 µm/min which compares favorably with legacy Sievert’s experiments in literature. Total percentage of the surface area hydrided after 242 min was 42.7%, and post-characterization of the UH 3 powders shows both α-UH 3 and β-UH 3 . This work highlights the strength of characterizing the early-stage uranium-hydrogen reaction using white-light interferometry, but more importantly, unifying the understanding and mechanism of the uranium-hydrogen reaction kinetics.

Materials science↗
NASA NTRS1982

Kinetics and mechanism of the oxidation process of two-component Fe-Al alloys

The oxidation process of two-component Fe-Al alloys containing up to 7.2% Al and from 18 to 30% Al was studied. Kinetic measurements were conducted using the isothermal gravimetric method in the range of 1073-1223 K and 1073-1373 K for 50 hours. The methods used in studies of the mechanism of oxidation included: X-ray microanalysis, X-ray structural analysis, metallographic analysis and marker tests.

Przewlocka, H.↗
DOE OSTI2022

Kinetics and Reaction Mechanisms of Acetic Acid Hydrodeoxygenation over Pt and Pt–Mo Catalysts

In this work, kinetic measurements for silica-supported Pt and Pt-Mo catalysts were collected in vapor-phase acetic acid hydrodeoxygenation by varying the hydrogen partial pressure between 18 and 72 kPa and acetic acid partial pressure between 7 and 18 kPa at 423-473 K. At all testing conditions, the Pt-Mo catalyst was more active and selective. In addition, the apparent activation energy for Pt-Mo of 76±3 kJ/mol was lower than that of 84±4 kJ/mol for Pt. The apparent reaction orders were also different. The order in hydrogen of 0.8±0.1 for Pt-Mo changed to zero at higher hydrogen partial pressures while that for Pt remained constant at 0.6±0.1. A near-zero order in acetic acid for Pt-Mo changed to -2.1 at higher acetic acid pressures while that for Pt remained constant at -2.9±0.3. These differences in reaction kinetics as well as in selectivity trends with changes in temperature and feed composition indicated a change in the reaction mechanism for Pt-Mo. The catalysts were characterized with hydrogen temperature programmed desorption, oxygen temperature programmed oxidation and transmission electron microscopy with energy-dispersed X-ray spectroscopy elemental mapping. Mo was present in the form of subnanometer-size clusters on the surface of Pt nanoparticles. Both Pt and Pt-Mo catalysts were stable under the reaction conditions for 10 h, and the size and structure of Pt and Pt-Mo particles remained mostly unchanged, without coke accumulation. Density functional theory calculations show that surface acetate is not a major reaction intermediate on both Pt and Pt-Mo and, instead, C-OH bond splitting with the formation of acetyl is the first reaction step in hydrodeoxygenation. The activation energy for this step is dramatically lower on Pt-Mo. Furthermore, the activity of acetyl on Pt-Mo is different. Unlike on pure Pt, the reaction of C-O bond splitting becomes exothermic with a lower activation energy on Pt-Mo, and the reaction of C-C bond splitting, in contrast, becomes endothermic with a higher activation energy, explaining the experimentally observed higher activities and selectivities of Pt-Mo. In addition, the calculations demonstrate that a pair of Pt-Mo surface atoms acts as a single active site where Mo serves as a preferential binding anchor for O atoms. The presence of Mo atoms changes the structure and energy of adsorbed and reacting surface species.

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

Sulfate adenylyl transferase kinetics and mechanisms of metabolic inhibitors of microbial sulfate respiration

Abstract Sulfate analog oxyanions that function as selective metabolic inhibitors of dissimilatory sulfate reducing microorganisms (SRM) are widely used in ecological studies and industrial applications. As such, it is important to understand the mode of action and mechanisms of tolerance or adaptation to these compounds. Different oxyanions vary widely in their inhibitory potency and mechanism of inhibition, but current evidence suggests that the sulfate adenylyl transferase/ATP sulfurylase (Sat) enzyme is an important target. We heterologously expressed and purified the Sat from the model SRM, Desulfovibrio alaskensis G20. With this enzyme we determined the turnover kinetics (kcat, KM) for alternative substrates (molybdate, selenate, arsenate, monofluorophosphate, and chromate) and inhibition constants (KI) for competitive inhibitors (perchlorate, chlorate, and nitrate). These measurements enable the first quantitative comparisons of these compounds as substrates or inhibitors of a purified Sat from a respiratory sulfate reducer. We compare predicted half-maximal inhibitory concentrations (IC50) based on Sat kinetics with measured IC50 values against D. alaskensis G20 growth and discuss our results in light of known mechanisms of sensitivity or resistance to oxyanions. This analysis helps with the interpretation of recent adaptive laboratory evolution studies and illustrates the value of interpreting gene–microbe–environment interactions through the lens of enzyme kinetics.

Carlson, Hans K. (ORCID:0000000215835313)↗
DOE OSTI2022

Multiscale Interaction of Turbulence, Temperature, and Soot Formation: Measurements for Critical Assessments of Chemical Kinetics and Mechanisms

This program targeted an improved understanding of how turbulence affects soot formation chemistry (directly and indirectly) with a particular focus on detailing the multiscale coupling between flow turbulence, mixing, thermal transport, and soot formation kinetics in gas-phase reacting systems. In this project, simultaneous, quantitative multi-dimensional velocity, soot volume fraction, and gas-phase temperature measurements in turbulent non-premixed sooting flames were developed. These new diagnostics tools can be used to elucidate the relative effects of fluid kinematics, mixing, thermal processes, and turbulence/scalar time/length scales on soot formation chemistry and topology. Simultaneous multi-parameter measurements were acquired within a series of flames with different Reynolds numbers and spatial locations to investigate the inter-dependence of soot, temperature, and turbulence within the soot inception, growth, and oxidation region. Preliminary assessment of the results has been completed at the project end and detailed analysis is planned following the completed program.

02 PETROLEUM↗
DOE OSTI2025

Combined TDLAS and chemiluminescence imaging in a flat flame burner operated with NH3/H2 blends

Ammonia is viewed as a viable hydrogen carrier due to favorable storage and transport characteristics. While it can be re-converted to hydrogen at point-of-use via thermal catalytic cracking, direct utilization in combustion systems can result in reduced costs and improved efficiency. A major barrier to this approach is the low flammability and potential for high nitrogen oxide emissions, driven by fuel-bound nitrogen and complex kinetic pathways. While a number of kinetic mechanisms currently exist for simulating ammonia combustion, a major need continues to be direct information about species profiles in easy-to-model systems capable of isolating chemical kinetics from multi-dimensional fluid dynamic effects. This paper reports on recent species measurements made in a flat flame burner using a combined tunable-diode-laser-absorption-spectroscopy (TDLAS) and chemiluminescence imaging approach. Three flame conditions were included representative of NH3/H2 blends, partially cracked NH3 (inc. N2), and 100% NH3 with enhanced air (30% oxygen). Two NIR distributed feedback (DFB) laser diodes were used to determine H2O concentration and temperature (via ratio thermometry) at various radial and axial positions, after which an inverse Abel transform was used to infer centerline values. Companion images were collected using a Princeton Instrument PI-MAX intensified camera equipped with a 105mm UV lens and multiple filter sets targeting OH*, NH*, and NH2* emission. Results were compared to companion Cantera burner-stabilized flame simulations using various kinetic mechanisms. A recent mechanism including excited species chemistry was also included, to investigate whether excited and ground state profiles exhibit significant differences.

ammonia combustion↗
DOE OSTI2020

Effects of fuel composition and octane sensitivity on polycyclic aromatic hydrocarbon and soot emissions of gasoline–ethanol blend surrogates

The sooting propensity of a fuel is closely coupled with the fuel composition and chemistry. A detailed understanding of their effects is, therefore, needed to develop next-generation fuels which can minimize particulate emissions. With this overarching goal, the present work numerically investigates the effects of fuel composition and octane sensitivity (S) on polycyclic aromatic hydrocarbons (PAH) and soot emissions, for four-component gasoline-ethanol blend surrogates comprising isooctane, n-heptane, toluene, and ethanol. A partially-premixed counterflow flame is chosen as the canonical configuration for this study and simulations are performed using CHEMKIN-Pro-employing a kinetic mechanism developed by Park et al. (2017). In addition, a, detailed soot model based on the sectional method is used to capture the spatial characteristics of soot emissions. The kinetic mechanism and soot model are validated using available experimental data for various targets. A total of 86 TPRF-E mixtures, spanning a wide range of concentration of each component, and a wide range of S are analyzed. The effect of each non-paraffinic fuel component on the resultant PAH and soot emissions is investigated. PAH and soot emissions are found to vary significantly depending upon the blend composition. Additionally, based on the parametric sweeps, a regression analysis is carried out to identify global parameters that govern the formation of PAHs and soot. The analysis shows that both toluene content and S have a prominent effect on the formation of PAHs and soot, with toluene content having a stronger impact. Moreover, larger PAHs have higher dependency on toluene content and S. Furthermore, a detailed analysis is carried out to understand the physical and chemical phenomena associated with the observed trends of PAH and soot emissions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1997

Kinetics and Mechanism of the Reaction of Hydoxyl Radicals with Acetonitrile under Atmospheric Conditions

The pulsed laser photolysis-pulsed laser induced fluorescence technique has been employed to determine absolute rate coefficients for the reaction OH + CH3CN (1) and its isotopic variants, OH + CD3CN (2), OD + CH3CN (3), and OD + CD3CN (4). Reactions 1 and 2 were studied as a function of pressure and temperature in N2, N2/O2, and He buffer gases. In the absence of O2 all four reactions displayed well-behaved kinetics with exponential OH decays and pseudo-first rate constants which were proportional to substrate concentration. Data obtained in N2 over the range 50-700 Torr at 298 K are consistent with k(sub 1), showing a small pressure dependence. The Arrhenius expression obtained by averaging data at all pressures in k(sub 1)(T) = (1.1(sup +0.5)/(sub -0.3)) x 10(exp -12) exp[(-1130 +/- 90)/T] cu cm /(molecule s). The kinetics of reaction 2 are found to be pressure dependent with k(sub 2) (298 K) increasing from (1.21 +/- 0.12) x 10(exp -14) to (2.16 +/- 0.11) x 10(exp -14) cm(exp 3)/ (molecule s) over the pressure range 50-700 Torr of N2 at 298 K. Data at pressures greater than 600 Torr give k(sub 2)(T) = (9.4((sup +13.4)(sub -5.0))) x 10(exp -13) exp[(-1180 +/- 250)/T] cu cm/(molecule s). The rates of reactions 3 and 4 are found to be independent of pressure over the range 50-700 Torr of N2 with 298 K rate coefficient given by k(sub 3) =(3.18 +/- 0.40) x 10(exp -14) cu cm/(molecule s) and k(sub 4) = (2.25 +/-0.28) x 10(exp -14) cu cm/(molecule s). In the presence of O2 each reaction shows complex (non-pseudo-first-order) kinetic behavior and/or an apparent decrease in the observed rate constant with increasing [O2], indicating the presence of significant OH or OD regeneration. Observation of regeneration of OH in (2) and OD in (3) is indicative of a reaction channel which proceeds via addition followed by reaction of the adduct, or one of its decomposition products, with O2. The observed OH and OD decay profiles have been modeled by using a simple mechanistic scheme to extract kinetic information about the adduct reations with O2 and branching ratios for OH regeneration. A plausible mechanism for OH regeneration in (2) involves OH addition to the nitrogen atom followed by O2 addition to the cyano carbon atom, isomeriazation and decomposition to D2CO + DOCN + OH. Our results suggest that the OH + CH3CN reaction occurs via a complex mechanism involving both bimolecular and termolecular pathways, analogous to the mechanisms for the the important atmospheric reactions of OH with CO and HNO3.

Hynes, A. J.↗
DOE OSTI2024

Microstructural Coarsening Kinetics and Mechanical Property Changes in Long-Term Aged Sn–Pb–Sb Solder Joints

Tin-lead-antimony (50Sn–47Pb–3Sb wt.%) soldered assemblies were mechanically tested approximately 30 years after initial production and found to have solder joints of reduced strength. The microstructure of this solder alloy exhibits a ternary eutectic structure with Sn-rich, Pb-rich, and SnSb phases. Accelerated aging was performed to evaluate solder microstructural coarsening and associated strength of laboratory solder joints to correlate these properties to the “naturally aged” solder joints. Isothermal aging was conducted at room temperature, 55, 70, 100, and 135 °C and aging times that ranged from 0.1 to 365 days. The coarsening kinetics of the Pb-rich phase were determined through optical microscopy and image analysis methods established in previous studies on binary Sn–Pb solder. A kinetic equation was developed with time exponent n of 0.43 and activation energy of 24000 J/mol, suggesting grain boundary diffusion or other fast diffusion pathways controlling the microstructural evolution. Compression testing and Vickers microhardness showed significant strength loss within the first 20–30 days after soldering; then, the microstructure and mechanical properties changed more slowly over long periods of time. Further, by combining accelerated aging data and the microstructure-based kinetics, strength predictions were made that match well with the properties of the actual soldered assemblies naturally aged for 30 years. However, aging at the highest temperature of 135 °C produced anomalous behavior suggesting that extraneous aging mechanisms are active. Therefore, data obtained at this temperature or higher should not be used. Overall, the combined microstructural and mechanical property methods used in this study confirmed that the observed reduction in strength of ~ 30-year-old solder joints can be accounted for by the microstructural coarsening that takes place during long-term solid-state aging.

36 MATERIALS SCIENCE↗
NASA NTRS1988

An atmospheric pressure flow reactor: Gas phase kinetics and mechanism in tropospheric conditions without wall effects

A new type of gas phase flow reactor, designed to permit the study of gas phase reactions near 1 atm of pressure, is described. A general solution to the flow/diffusion/reaction equations describing reactor performance under pseudo-first-order kinetic conditions is presented along with a discussion of critical reactor parameters and reactor limitations. The results of numerical simulations of the reactions of ozone with monomethylhydrazine and hydrazine are discussed, and performance data from a prototype flow reactor are presented.

Koontz, Steven L.↗
DOE OSTI2024

Kinetics and Mechanism of Ce(IV) Phase Transfer by the Neutral Extractants Tributyl Phosphate and N,N -Di(2-ethylhexyl)isobutyramide

Tributyl phosphate and N,N-di(2-ethylhexyl)isobutyramide (DEHiBA) are uranium-selective extractants that could be used to recover low-enriched uranium from commercial used nuclear fuel. The economic viability of liquid-liquid extraction processes for chemical separations depends on both thermodynamic and kinetic considerations. Here we used microfluidic droplet extraction to measure interfacial phase transfer rate constants for the extraction and stripping of Ce(IV), a non-radioactive actinide surrogate. The Damkohler numbers for each system were calculated and the phase transfer processes were determined to be diffusion-limited under all conditions, contrary to prior studies using constant interface stirred cells and single drop methods. A well-extracted 2:1 DEHiBA/Ce(IV) complex in the organic phase was determined from batch distribution studies, suggesting a different extraction mechanism for Ce(IV) compared with poorly extracted Pu(IV). Finally, phase disengagement rates were found to be rapid in both systems, in agreement with other studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1972

Kinetics and mechanism of the formation of water cluster ions from O2(plus) and H2O in He, Ar, N2, and O2 at 296 K

The reaction sequence leading from O2(+) to H3O(+)-H2O was examined in He, Ar, N2 and O2 carrier gases in a flowing afterglow system. The rate constants for the reactions were measured and the kinetic analysis for their determination is presented. For M = N2, two new steps involving the formation and reaction of O2(+)-N2 were proposed and examined. The rate constants are discussed and compared with other experimental values.

Howard, C. J.↗
DOE OSTI2023

Kinetics and Mechanism of Tetravalent Cerium Extraction by Di-2-Ethylhexyl Isobutyramide (DEHiBA)

DEHiBA is a fully-incinerable, CHON extractant with a high selectivity for hexavalent actinides. However, as a recently-developed ligand, much remains unknown about its physical and chemical properties, including its extraction and phase disengagement rates. Here, we present data on the phase transfer kinetics of Ce(IV) extraction and stripping by both DEHiBA and TBP collected using microfluidic devices. Ce(IV) was selected as a surrogate for Pu(IV) and Np(IV) in the initial tests of the microfluidics system prior to testing with the actinides. Pseudo first-order reaction rate constants are determined for both systems, and the corresponding Damköhler numbers (Da) are calculated to establish whether the extraction and stripping processes are kinetically or diffusion controlled. The stoichiometry of the extracted Ce(IV)-DEHiBA complex is determined, and the phase disengagement properties under extraction conditions are assessed using the dimensionless dispersion number. A possible explanation for the favorable extraction of Ce(IV) by DEHiBA, which is known to poorly extract many tetravalent cations, is presented.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗