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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
NASA NTRS2010

Kinetic Re-Evaluation of Fuel Neutralization by AKGA

Baseline characterization testing previously identified alpha-ketoglutaric acid (AKGA) cis a potential alternative to the current standard hydrazine (HZ) family fuel neutralization techniques in use at Kennedy Space Center (KSC). Thus far, the reagent shows promise for use in hardware decontamination operations and as a drop-in replacement for the scrubber liquor currently used in KSC four tower vapor scrubbers. Implementation of AKGA could improve process safety and reduce or eliminate generation of hydrazine-Iaden waste streams. This paper focuses on evaluation of the kinetics of these decontamination reactions in solution. Pseudo first order reaction rate constants with respect to the pyridazine products (6-oxo-4,5-dihydro-1H-pyridazine-3-carboxylic acid, (PCA) and 1-methyl-6-oxo-4,5-dihydro-pyridazine-3-carboxylic acid (mPCA)) in the presence of excess AKGA were determined by monitoring product formation using a ultra-violet visible absorption spectroscopy method. The results are presented here in comparison to previous data obtained by monitoring reactant depletion by gas chromatography with nitrogen phosphorus detector (GC-NPD).

Oropeza Cristina↗
DOE OSTI2020

Applicability of the Delplot method for the determination of catalytic reaction sequences: Hydrodeoxygenation of $\gamma$-valerolactone on Ni 2 P/MCM-41

Contact-time measurements based on sites are used to investigate the reaction sequence of the hydrodeoxygenation of γ-valerolactone (GVL) on Ni 2 P/MCM-41. Here the study is carried out at 300 °C and 0.5 MPa with site times of 0.29–6.1 s. A reaction network is proposed in which pentanoic acid and 2-methyltetrahydrofuran (2-MTHF) are formed in parallel initially and pentanal, butane and pentane are formed subsequently. A first-rank Delplot analysis (selectivity) gives a good fit, but higher-rank Delplots do not. The lack of applicability is explained by the magnitude of the rate constants, in which the rate constant for one of the later steps (the consumption of pentanal) is substantially larger than those for the preceding steps. For this reason, pentanal demonstrated the characteristics of a primary product and consequently affected the discrimination of higher rank products. A simulation of a model sequence with assumed rate constants confirms the reason why the Delplot method does not work for this reaction. Since the rate constants cannot be determined a priori to be of close magnitude, the Delplot method cannot be generally used to ascertain reaction sequences.

42 ENGINEERING↗
NASA NTRS1980

Pressure dependence of the absolute rate constant for the reaction OH + C2H2 from 228 to 413K

The pressure dependence of absolute rate constants for the reaction of OH + C2H2 yields products has been examined at five temperatures ranging from 228 to 413 K. The experimental techniques which was used is flash photolysis-resonance fluoresence. OH was produced by water photolysis and hydroxyl resonance fluorescent photons were measured by multiscaling techniques. The results indicate that the low pressure bimolecular rate constant is 4 x 10 the the minus 13th power cu cm molecule (-1) s(-1) over the temperature range studied. A substantial increase in the bimolecular rate constant with an increase in pressure was observed at all temperatures except 228 K. This indicates the importance of initial adduct formation and subsequent stablization. The high pressure results are well represented by the Arrhenius expression (k sub bi) sub infinity = (6.83 + or - 1.19) x 10 to the minus 12th power exp(-646 + or - 47/T)cu cm molecule (-1) s(-1). The results are compared to previous investigated and are theoretically discussed. The implications of these results on modeling of terrestrial and planetary atmospheres and also in combustion chemistry are discussed.

Michael, J. V.↗
NASA NTRS2017

Development of a Detailed Surface Chemistry Framework in DSMC

Many of the current direct simulation Monte Carlo (DSMC) codes still employ only simple surface catalysis models. These include only basic mechanisms such as dissociation, recombination, and exchange reactions, without any provision for adsorption and finite rate kinetics. Incorporating finite rate chemistry at the surface is increasingly becoming a necessity for various applications such as high speed re-entry flows over thermal protection systems (TPS), micro-electro-mechanical systems (MEMS), surface catalysis, etc. In the recent years, relatively few works have examined finite-rate surface reaction modeling using the DSMC method.In this work, a generalized finite-rate surface chemistry framework incorporating a comprehensive list of reaction mechanisms is developed and implemented into the DSMC solver SPARTA. The various mechanisms include adsorption, desorption, Langmuir-Hinshelwood (LH), Eley-Rideal (ER), Collision Induced (CI), condensation, sublimation, etc. The approach is to stochastically model the various competing reactions occurring on a set of active sites. Both gas-surface (e.g., ER, CI) and pure-surface (e.g., LH, desorption) reaction mechanisms are incorporated. The reaction mechanisms could also be catalytic or surface altering based on the participation of the bulk-phase species (e.g., bulk carbon atoms). Marschall and MacLean developed a general formulation in which multiple phases and surface sites are used and we adopt a similar convention in the current work. Microscopic parameters of reaction probabilities (for gas-surface reactions) and frequencies (for pure-surface reactions) that are require for DSMC are computed from the surface properties and macroscopic parameters such as rate constants, sticking coefficients, etc. The energy and angular distributions of the products are decided based on the reaction type and input parameters. Thus, the user has the capability to model various surface reactions via user-specified reaction rate constants, surface properties and parameters.

Gas↗
NASA NTRS1989

Degradation and crosslinking of perfluoroalkyl polyethers under X-ray irradiation in ultrahigh vacuum

Degradation of three types of commercially available perfluoroalkyl polyethers (PFPE)-Demnum S200, Fomblin Z25, and Krytox 16256-by X-ray irradiation was studied by using X-ray photoemission spectroscopy (XPS) and a mass spectrometer under ultra-high-vacuum conditions. The carbons in the polymers were characterized by chemical shifts of Cls binding energies. Gaseous products containing COF2 and low-molecular-weight fluorocarbons were formed. From Fomblin Z25, which has acetal linkages (-OCF2O-), a large quantity of COF2 gas was evolved. Liquid products became tacky after a long irradiation time, and some did not dissolve in Freon. High-pressure liquid chromatography (HPLC) showed that molecular weight distribution became broader and that higher molecular weight polymers were formed from Demnum and Krytox. We concluded from these results that degradation and cross-linking took place simultaneously. Demnum crosslinked more easily than the other fluids. The time dependence of both XPS spectra of Cls and mass spectra showed that C-O-bonded carbons in PFPE'S were removed faster than other carbons. There was no substrate effect on the degradation reaction because the first-order rate constants calculated from the change of gaseous products were similar when stainless steel (440C) and gold-coated surfaces were used. Metal fluorides were formed on stainless steel during the reaction. A mechanism for the degradation of PFPE'S is discussed on the basis of their molecular structures.

Mori, Shigeyuki↗
NASA NTRS1980

The chemistry of excited NO/+/ in an aurora

The six most significant production and seven most significant loss mechanisms are identified for NO(+)(a3 Sigma) in the aurora. Rate constants are given for these reactions as well as for the 14 most important reactions competing with the production of NO(+)(a). Using available data and certain crucial deductions on chemical reaction rates to simulate a number of altitude profiles, it is concluded that the two predominant sources of NO(+)(a3 Sigma) are probably N(+) + O2 yields NO(+)(a) + O and N2(+) + NO yields NO(+)(a) + N2. Radiative decay is not the primary loss mechanism but can dominate above 150 km. Destruction via charge exchange with N2 and O are most important below 150 km.

Young, E. R.↗
DOE OSTI2024

Electron transfer in a crystalline cytochrome with four hemes

Diffusion of electrons over distances on the order of 100 μm has been observed in crystals of a small tetraheme cytochrome (STC) from Shewanella oneidensis [J. Huang et al . J. Am. Chem. Soc. 142, 10459–10467 (2020)]. Electron transfer between hemes in adjacent subunits of the crystal is slower and more strongly dependent on temperature than had been expected based on semiclassical electron-transfer theory. Here, in this work, we explore explanations for these findings by molecular-dynamics simulations of crystalline and monomeric STC. New procedures are developed for including time-dependent quantum mechanical energy differences in the gap between the energies of the reactant and product states and for evaluating fluctuations of the electronic-interaction matrix element that couples the two hemes. Rate constants for electron transfer are calculated from the time- and temperature-dependent energy gaps, coupling factors, and Franck–Condon-weighted densities of states using an expression with no freely adjustable parameters. Back reactions are considered, as are the effects of various protonation states of the carboxyl groups on the heme side chains. Interactions with water are found to dominate the fluctuations of the energy gap between the reactant and product states. The calculated rate constant for electron transfer from heme IV to heme Ib in a neighboring subunit at 300 K agrees well with the measured value. However, the calculated activation energy of the reaction in the crystal is considerably smaller than observed. We suggest two possible explanations for this discrepancy. The calculated rate constant for transfer from heme I to II within the same subunit of the crystal is about one-third that for monomeric STC in solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1982

A photochemical study of the kinetics of the reactions of NH2 with phosphine, ethylene, and acetylene using flash photolysis-laser induced fluorescence

The photochemistry of the reactions of NH2 was investigated in an attempt to explain the existence of an abundance of ammonia in the Jovian atmosphere. The production of ammonia reservoirs from the coupling of ammonia with other atmospheric constituents was considered. The rate constants for the reactions of NH2 radicals with phosphine, acetylene, and ethylene were measured. Flash photolysis was used for the production of NH2 radicals and laser induced fluorescence was employed for radical detection. It was determined that the rates of the reactions were too slow to be significant as a source of ammonia reservoirs in the Jovian atmosphere.

Bosco, S. R.↗
DOE OSTI2021

Microalgae Conversion to Biofuels and Biochemical via Sequential Hydrothermal Liquefaction (SEQHTL) and Bioprocessing: 2020 State of Technology

A preliminary techno-economic analysis (TEA) was developed for the fiscal year 2020 state of technology (SOT) assessment to evaluate the benefits and risks for a large-scale microalga hydrothermal liquefaction (HTL) system based on most recent testing results. The focus of the study is directed toward the conversion system, which consists of five processes: two-stage sequential HTL (SEQHTL), biocrude upgrading to final fuels, bioprocessing for co-product generation, hydrogen generation, and steam cycle. In this system, algae biomass with corn stover supplement during the lower algae productivity seasons (winter, fall, and spring) to match the maximum algae seasonal production rate in summer is employed to maintain a constant plant capacity in all the seasons. Algae only (summer season) or algae/corn stover blended feedstock (other seasons) are sent to a two-stage SEQHTL process. In stage I, the carbohydrates in the feedstock are extracted and separated from the residual solid. The residual solid from stage I is further converted to biocrude in the SEQHTL stage II step. The biocrude is upgraded to final fuel products in an upgrading process. The extract stream from HTL stage I is sent to the bioprocessing section for co-product generation via fermentation of carbohydrate. Lactic acid (LA) is assumed to be the co-product based on current bioprocessing testing results.

09 BIOMASS FUELS↗
DOE OSTI2021

Substitution Reactions in the Pyrolysis of Acetone Revealed through a Modeling, Experiment, Theory Paradigm

The development of high-fidelity mechanisms for chemically reactive systems is a challenging process that requires the compilation of rate descriptions for a large and somewhat ill-defined set of reactions. The present unified combination of modeling, experiment, and theory provides a paradigm for improving such mechanism development efforts. Here we combine broadband rotational spectroscopy with detailed chemical modeling based on rate constants obtained from automated ab initio transition state theory-based master equation calculations and high-level thermochemical parametrizations. Broadband rotational spectroscopy offers quantitative and isomer-specific detection by which branching ratios of polar reaction products may be obtained. Using this technique, we observe and characterize products arising from H atom substitution reactions in the flash pyrolysis of acetone (CH 3 C(O)CH 3 ) at a nominal temperature of 1800 K. The major product observed is ketene (CH 2 CO). Minor products identified include acetaldehyde (CH 3 CHO), propyne (CH 3 CCH), propene (CH 2 CHCH 3 ), and water (HDO). Literature mechanisms for the pyrolysis of acetone do not adequately describe the minor products. The inclusion of a variety of substitution reactions, with rate constants and thermochemistry obtained from automated ab initio kinetics predictions and Active Thermochemical Tables analyses, demonstrates an important role for such processes. Furthermore, the pathway to acetaldehyde is shown to be a direct result of substitution of acetone's methyl group by a free H atom, while propene formation arises from OH substitution in the enol form of acetone by a free H atom.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1979

Physical models of Comet Halley based upon qualitative data from the 1910 apparition

A semi-empirical theory was developed, tying the hydrogen production rate of a comet to its visual light curve. Two unknown constants, which are essentially the efficiencies of these two processes, are derived from the comets for which quantitative data exist. This theory has been applied to P/Halley, using the light curve of Yeomans, which was derived from the original 1910 observations, with aperture corrections applied. Given the hydrogen production rate, it is assumed that N(H20) = 0.5 N(H) and that there is 0.2 N(H20) of other species. From several converging lines of evidence the mass of dust is taken as half the mass of gas. The Sekanina-Miller distribution function of particle size is used. Particle velocities are calculated using Delsemmes version of the Probstein theory. From these, near nucleus dust density, flux, etc. are calculated. Dust envelope sizes are calculated from the old mechanical theory of tails. Extreme models are calculated from the old mechanical theory of tails. Extreme models are also furnished based upon a "sum-of-negative-tolerance" approach.

Newburn, R. L.↗
NASA NTRS2018

Development of a Detailed Surface Chemistry Framework in DSMC

A generalized finite-rate surface chemistry framework incorporating a comprehensive list of reaction mechanisms is developed and implemented into the Direct Simulation Monte Carlo (DSMC) solver SPARTA (Stochastic PArallel Rarefied-gas Time-accurate Analyzer). The various mechanisms include adsorption, desorption, Eley-Rideal (ER), and several types of Langmuir-Hinshelwood (LH) mechanisms. The approach is to stochastically model the various competing reactions occurring on a set of active sites. Both gas-surface (e.g., adsorption, ER) and pure-surface (e.g., desorption) reaction mechanisms are incorporated, and the framework also includes catalytic or surface altering mechanisms involving the participation of the bulk-phase species (e.g., bulk carbon atoms). Marschall and MacLean developed a general formulation in which multiple phases and surface sites are used and a similar convention is adopted in the current work. Expressions for the microscopic parameters of reaction probabilities (for gas-surface reactions) and frequencies (for pure-surface reactions) that are required for DSMC are derived from the surface properties and macroscopic parameters such as rate constants, sticking coefficients, etc. The energy and angular distributions of the products are specified according to the reaction type and input parameters. This framework also presents physically consistent procedures to accurately compute the reaction probabilities and frequencies in the case of multiple reactions. The result is a modeling tool with a wide variety of surface reactions characterized via user-specified reaction rate constants, surface properties and parameters.

Surface Chemistry↗
NASA NTRS1985

Experimental studies on the reaction kinetics of 1,1-dimethylhydrazine and oxygen

Measurements behind shock waves in highly diluted 1,1 dimethylhydrazine-O2-Ar mixtures clearly showed a two-stage reaction. In the first stage, UDMH decomposes via a unimolecular step; in the second stage, clearly separated from the first one, the decay products react further with O2. Values for the rate constant of unimolecular decomposition were obtained.

Just, T.↗
NASA NTRS2004

Measured and modeled HOCl profiles in the mid-latitude stratosphere : implication for ozone loss

The HOCl catalytic cycle is an efficient ozone loss mechanism in the lower mid-latitude stratosphere. We use a diurnal steady-state photochemical model to calculate profiles of HOCl for conditions encountered by a number of high-altitude balloon flights. To assess how well this model represents ozone loss by the HOCl cycle, we compare our calculations of HOCl and its precursors Cl0 and HO2 with measurements obtained by an FTIR solar absorption spectrometer (MkIV), a far-infrared emission spectrometer (FIRS-2), and a submillimetenvave limb sounder (SLS). We then evaluate these comparisons in light of a number of recent laboratory studies of the main formation mechanism of HOCl, the reaction of Cl0 + HO2. Those studies measured both the reaction rate constant and the quantum yield for a second product pathway, formation of HCl.

stratosphere↗
NASA NTRS2021

Testing Short-term Variability and Sampling of Primary Volatiles in Comet 46P/Wirtanen

The exceptionally favorable close approach of Jupiter-family comet 46P/Wirtanen in 2018 December enabled characterization of its primary volatile composition with exceptionally high spatial resolution and sensitivities using the iSHELL spectrograph at the NASA Infrared Telescope Facility on Maunakea, HI. We sampled emissions from H2O, HCN, C2H2, NH3,C2H6, and CH3OH on UT 2018 December 21 using two instrumental settings that spanned the 2.9–3.6μm spectral region. We also obtained a sensitive 3σupper limit for H2CO and for the rarely studied molecule HC3N. We report rotational temperatures, production rates, and mixing ratios(relative to H2O as well as to C2H6). We place our results in context by comparing them with other comets observed at near-IR wavelengths. We also compare our results with those obtained using the NIRSPEC-2 spectrograph on Keck II on UT December 17 and 18 and with results obtained from iSHELL on other dates during the same apparition. Within1–2σ uncertainty, production rates obtained for all molecules in this work were consistent with those obtained using NIRSPEC-2 except H2O, indicating low-level variability on a timescale of days. Mixing ratios with respect to H2O in 46P/Wirtanen were consistent with corresponding values from NIRSPEC-2 within the uncertainty with the exception of CH3OH, which yielded a higher ratio on December 21. Our measurements afforded a high temporal resolution that spanned∼2/3 of the rotational period of 46P/Wirtanen, enabling us to test short-term variability in the production rates of H2O and HCN due to rotational effects. Both H2O and HCN production rates showed similar temporal variability, resulting in nearly constant HCN/H2O

Younas Khan↗
NASA NTRS2001

Ecophysiological Changes in Microbial Mats Incubated in a Greenhouse Collaboratory

Microbial mats are modern examples of the earliest microbial communities known. Among the best studied are microbial mats growing in hypersaline ponds managed for the production of salt by Exportadora de Sal, S.A. de C.V., Guerrero Negro, Baja California Sur, Mexico. In May, 2001, we collected mats from Ponds 4 and 5 in this system and returned them to Ames Research Center, where they have been maintained for a period of over nine months. We report here on both the ecophysiological changes occurring in the mats over that period of time as well as the facility in which they were incubated. Mats (approximately 1 sq. meter total area) were incubated in a greenhouse facility modified to provide the mats with natural levels of visible and ultraviolet radiation as well as constantly flowing, temperature-controlled water. Two replicated treatments were maintained, a 'high salinity' treatment (about 120 ppt) and a 'low salinity' treatment (about 90 ppt). Rates of net biological activity (e.g., photosynthesis, respiration, trace gas production) in the mats were relatively constant over the several months, and were similar to rates of activity measured in the field. However, over the course of the incubation, mats in both treatments changed in physical appearance. The most obvious change was that mats in the higher salinity treatments developed a higher proportion of carotenoid pigments (relative to chlorophyll), resulting in a noticeably orange color in the high salinity mats. This trend is also seen in the natural salinity gradient present at the field site. Changes in the community composition of the mats, as assayed by denaturing gradient gel electrophoresis (DGGE), as well as biomarker compounds produced in the mats were also monitored. The degree to which the mats kept in the greenhouse changed from the originally collected mats, as well as differences between high and low salinity mats will be discussed. Additional information is contained in the original extended abstract.

Bebout, Brad↗
NASA NTRS1979

Reaction rate and products for the reaction O/3P/ + H2CO

A study of reaction kinetics of O + H2CO in a discharge-flow system using mass spectrometric detection of reactants and products is presented. It was performed under both oxygen-atom-rich and formaldehyde-rich conditions over the 296 to 437 K range, showing that the global bimolecular rate constant is in agreement with other studies. This study differs from others in that the reaction products can be observed, and a substantial yield of a primary reaction product was measured with a mass spectral peak at m/e=44. This suggests that the global reaction rate probably consists of combination, as well as of simple abstraction. For the combination, one hypothesis is that triplet dioxymethylene is formed which polymerizes to triplet formic acid; the vibrationally excited triplet formic acid may decompose to form several sets of products, including HCO + OH and HCO2 + H.

Chang, J. S.↗
NASA NTRS1984

Injection-induced turbulence in stagnation-point boundary layers

A theory is developed for the stagnation point boundary layer with injection under the hypothesis that turbulence is produced at the wall by injection. From the existing experimental heat transfer rate data obtained in wind tunnels, the wall mixing length is deduced to be a product of a time constant and an injection velocity. The theory reproduces the observed increase in heat transfer rates at high injection rates. For graphite and carbon-carbon composite, the time constant is determined to be 0.0002 sec from the existing ablation data taken in an arc-jet tunnel and a balistic range.

Park, C.↗