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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 NTRS1984

Pressure and temperature dependence of the reaction NO2 + NO3 + M yields N2O5 + M

The pressure and temperature dependences of the reaction NO2 + NO3 + M which yields N2O5 + M are investigated by using the flash photolysis/visible absorption technique in which the pseudo-first-order decay of NO3 is monitored as a function of total pressure (20-700 torr), diluent gas (M = He and N2), and temperature (236-358 K). The reaction is found to be in the falloff region in the 20-700 torr pressure range with collision efficiencies increasing in the order He less than N2. Falloff parameters are obtained by fitting the experimental data to the falloff equation of Troe and co-workers. The expression for k1(N2 concentration, T) is obtained and compared with the evaluations presented in the NASA (DeMore, 1983) and CODATA (Baulch et al., 1982) reviews of kinetic data for atmospheric chemistry. Both evaluations are based on N2O5 thermal decomposition data coupled with estimates of the equilibrium constant. The significance of the reactions for atmospheric chemistry rests not only on their rates but on the extent to which they result in a permanent sink for NOX.

Kircher, C. C.↗
NASA NTRS1982

Global-scale weekly and monthly energetics during January and February 1979

Time averages of the latitudinal distribution of kinetic energy and terms of the kinetic energy equation are presented as depicted by analyses of the First GARP Global Experiment during the First Special Observing Period. It is found that the monthly averages exhibit peaks in the stationary wave energy at 30 degrees N and in the tropics, while global decompositions of the streamfunction and velocity potential in spherical harmonics are truncated at the fourth degree. The kinetic energy distribution of the associated wind field displays peaks in the tropics and northern mid-latitudes in January, but only a tropical peak in February. These analyses support the Eliassen-Palm relationship for latitudinal momentum and geopotential wave transport, particularly in the mid-latitudes. However, in the deep tropics, latitudinal convergence of the fully resolved stationary wave momentum transport accompanies latitudinal convergence of stationary wave geopotential flux in westerly flow.

Paegle, J.↗
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.↗
NASA NTRSDate not supplied

A Multiphysics Study to Improve Specific Energy of Primary Batteries for Low Temperature Operation for Deep Space Missions

Several lander missions on the outer planets such as Europa, Enceladus, and Titan require electrical power to operate scientific and communication equipment. The traditional power generation methods, such as a photovoltaic array, are not feasible as their efficiency drops significantly at these vast distances. The novel radioisotope power systems are not practical today based on current lander designs and the effectiveness of these systems. To perform in situ science on distant planets, a high specific energy battery (>700 Wh/kg) needs to operate for about 480 hours under cold temperatures (-40C or 0C) [1]. While a primary battery such as Li-CFx can provide high specific energy at room temperature, its specific capacity decreases significantly at low temperatures. One of the causes for this drop is low ion and electrical conductivity, and slower reaction kinetics. Slower transport and facile kinetics lead to an increase in the battery’s resistance and higher voltage drops during the cell operation, thus reducing specific capacity. Both the transport and kinetics show a strong dependence on temperature. Thus, a small temperature rise can lead to an increase in the reaction rate and ion conductivity; since the temperature, cell resistance, and specific capacity are interdependent. A conventional battery model accounts for ohmic, thermodynamic, and, electrochemical, and chemical decomposition heating. The ohmic heating can be controlled by designing a resistive microstructure and varying the ratios of the active materials [2]. The kinetics can be improved by increasing the surface area, reducing the particle size, or adding a catalyst. These parameters are often optimized to achieve high specific energy at room temperatures. A similar optimization study is not available at low temperatures and for a primary (high specific energy) battery. For this presentation, we will explore the effect of geometrical, microstructural, and material properties on optimal specific capacity at low temperatures through multiphysics simulations. The ion transport resistance depends on the porosity and the tortuosity of an electrode and the separator.

M. Mehta↗
NASA NTRS1974

Kinetics of the reaction of nitric oxide with hydrogen

Mixtures of NO and H2 diluted in argon or krypton were heated by incident shock waves, and the infrared emission from the fundamental vibration-rotation band of NO at 5.3 microns was used to monitor the time-varying NO concentration. The reaction kinetics were studied in the temperature range 2400-4500 K using a shock-tube technique. The decomposition of nitric oxide behind the shock was found to be modeled well by a fifteen-reaction system. A principle result of the study was the determination of the rate constant for the reaction H + NO yields N + OH, which may be the rate-limiting step for NO removal in some combustion systems. Experimental values of k sub 1 were obtained for each test through comparisons of measured and numerically predicted NO profiles.

Flower, W. L.↗
NASA NTRS1999

Modeling and Real-Time Process Monitoring of Organometallic Chemical Vapor Deposition of III-V Phosphides and Nitrides at Low and High Pressure

The purpose of this paper is to review modeling and real-time monitoring by robust methods of reflectance spectroscopy of organometallic chemical vapor deposition (OMCVD) processes in extreme regimes of pressure. The merits of p-polarized reflectance spectroscopy under the conditions of chemical beam epitaxy (CBE) and of internal transmission spectroscopy and principal angle spectroscopy at high pressure are assessed. In order to extend OMCVD to materials that exhibit large thermal decomposition pressure at their optimum growth temperature we have designed and built a differentially-pressure-controlled (DCP) OMCVD reactor for use at pressures greater than or equal to 6 atm. We also describe a compact hard-shell (CHS) reactor for extending the pressure range to 100 atm. At such very high pressure the decomposition of source vapors occurs in the vapor phase, and is coupled to flow dynamics and transport. Rate constants for homogeneous gas phase reactions can be predicted based on a combination of first principles and semi-empirical calculations. The pressure dependence of unimolecular rate constants is described by RRKM theory, but requires variational and anharmonicity corrections not included in presently available calculations with the exception of ammonia decomposition. Commercial codes that include chemical reactions and transport exist, but do not adequately cover at present the kinetics of heteroepitaxial crystal growth.

Bachmann, K. J.↗
NASA NTRS2001

Trioxane-Air Counterflow Diffusion Flames in Normal and Microgravity

Trioxane, a weakly bound polymer of formaldehyde (C3H6O3, m.p. 61 C, b.p. 115 C), is a uniquely suited compound for studying material flammability. Like many of the more commonly used materials for such tests (e.g., delrin, polyethylene, acrylic sheet, wood, and paper), it displays relevant phenomena (internal heat conduction, melting, vaporization, thermal decomposition, and gas phase reaction of the decomposition products). Unlike the other materials, however, it is non-sooting and has simple and well-known chemical kinetic pathways for its combustion. Hence it should prove to be much more useful for numerical modeling of surface combustion than the complex fuels typically used. We have performed the first exploratory tests of trioxane combustion in the counterflow configuration to determine its potential as a surrogate solid fuel which allows detailed modeling. The experiments were performed in the spring and summer of 1998 at the National Institute of Standards and Technology in Gaithersburg, MD, and at NASA-GRC in Cleveland. Using counterflow flames at 1-g, we measured the fuel consumption rate and the extinction conditions with added N2 in the air; at mg conditions, we observed the ignition characteristics and flame shape from video images. We have performed numerical calculations of the flame structure, but these are not described here due to space limitations. This paper summarizes some burning characteristics of trioxane relevant to its use for studying flame spread and fire suppression.

Linteris, Gregory T.↗
NASA NTRS1972

Liquid propellant rockets.

A brief overview of the state of knowledge in liquid rocket technology is presented and examples are provided of instances where some fundamental principles of chemistry, fluid mechanics, and mathematics can be applied. A liquid propellant rocket classification is discussed together with rocket system performance, applications for liquid propellants, the effective exhaust velocity, aspects of simplified nozzle expansion, questions about theoretical propellant performance, the effect of chamber pressure on equilibrium performance, and the kinetic recombination in nozzles. Details of propellant combustion are examined, giving attention to propellant injection, evaporation-controlled combustion, combustion instability, and monopropellant decomposition.

Dipprey, D. F.↗
NASA NTRS2022

Recommended Direct Simulation Monte Carlo Collision Model Parameters for Reacting Methane Flows

While hydrocarbon combustion and gas-surface interactions have been simulated for a variety of applications in continuum solvers, such processes have been rarely investigated in Direct Simulation Monte Carlo (DSMC). Thus Variable Hard/Soft Sphere (VHS/VSS)collision parameters are not available for most molecules of interest in the decomposition of methane, a significant pyrolysis gas product and potential atmospheric species for Titan re-entries. As these properties are essential for accurate modeling of gas transport and thermochemical effects, a method must be devised to compute them for use in DSMC. In this study, the methodology outlined in Stephani et al is utilized to compute the VHS/VSS parameters by fitting the Ω(1,1)and Ω(2,2) collision integrals [1]. These collision integrals are typically computed from intermolecular potentials and are used in CFD simulations to calculate transport properties such as viscosity, thermal conductivity, and diffusion. This approach ensures consistency between micro-scale collisions and macro-scale transport properties. To produce the necessary collision integrals needed for the fitting routine, we utilize the method described by Laricchiuta et al, where collision integrals are computed based on the constituent particles’ polarizability and effective electron number [2].Preliminary computations of pure-species Ω(1,1)and Ω(2,2)collision integrals produced from the coupled approach of Stephani et al and Laricchiuta et al for methane show good agreement with those computed via available ab-initio Potential Energy Surface Computations, as seen in Figure 1. Above 300K, no more than 12% deviation is observed between the two results over the temperature range of the fitted PES data [3].Current results of this study include full collision-specificVSS transport properties for a complex-species mixture involving major byproducts of pure methane decomposition. Targeted final results will include a comprehensive list of VSS parameters relevant toDSMC simulations of Titan atmospheric entry, based on the reduced kinetic model of Savajano et al [4].

M R Gosma↗
NASA NTRS1995

Kinetics of FO2 with NO, NO2, O3, CH4, and C2H6

The presence of fluorine containing compounds (e.g. HF and COF2) in the Earth's atmosphere is thought to be due solely to the decomposition of man-made chemicals such as chlorofluorocarbons and hydrofluorocarbons. The effect on atmosphere ozone of reactive fluorine-containing intermediates produced during CFC and HFC decomposition has attracted significant interest recently.

fluorine compounds atmospheric gasses ozone mass s↗
NASA NTRS1979

The Production of Solar Cell Grade Silicon from Bromosilanes

A continuous Flow Reactor (CFR) process based on the hydrogen reduction of the bromosilanes SiBr4 and SiHBr3 was proposed. Initial experiments carried and directed at obtaining overall yield data for bromosilane reduction in the CFR, indicated the need for increased reactor residence time and deposition substrate particle packing density to fully characterize the kinetics (rate) and thermodynamics (yield) of observed silicon production. Fluidized bed experiments were therefore initiated to overcome these experimental difficulties, which showed both thermal decomposition and hydrogen reduction of SiHBr3 in a fluid bed reactor to present attractive closed-loop processes for producing solar cell grade polycrystalline silicon. No process selection could be made however due to the fact that preliminary optimization of 2 of 3 process stages in each case during the course of the experimental program showed comparable attainment of cost element objectives.

Schumacher, J. C.↗
NASA NTRS1971

Kinetics of the O plus O3 reaction

The gas phase reaction O + O3 yields 2 O2 was studied directly in a flow system under conditions of excess ozone, with O-atoms produced by thermal decomposition of Ar-O3 mixtures on a Nernst Glower, and measurement of the spatial O-atom decay by O + NO chemiluminescence with small, variable NO additions. The rate constant was found to be (9.6 + or - 0.7) x 10 to the minus 15th power cu/cm/molecule/sec at 298 K. Over the temperature range 269 to 409 K a rate expression (1.78 + or - 0.28) x 10 to the 11th power exp((-4.46 + or - 0.10 kcal/mole)/RT) is reported. The effects of interference by O2 (delta sub g) and product excitation are discussed, and the present results are compared with earlier investigations.

Mccrumb, J. L.↗
NASA NTRS1988

Hydrazine vapor detonations

The detonation velocity and cell widths for hydrazine decomposition were measured over a wide range of temperatures and pressures. The detonation velocity in pure hydrazine was within 5 percent of the calculated C-J velocity. The detonation cell width measurements were interpreted using the Zeldovich-Doering-von Neumann model with a detailed reaction mechanism for hydrazine decomposition. Excellent agreement with experimental data for pure hydrazine was obtained using the empirical relation that detonation cell width was equal to 29 times the kinetically calculated reaction zone length.

Pedley, M. D.↗
NASA NTRS2008

Simplified Modeling of Oxidation of Hydrocarbons

A method of simplified computational modeling of oxidation of hydrocarbons is undergoing development. This is one of several developments needed to enable accurate computational simulation of turbulent, chemically reacting flows. At present, accurate computational simulation of such flows is difficult or impossible in most cases because (1) the numbers of grid points needed for adequate spatial resolution of turbulent flows in realistically complex geometries are beyond the capabilities of typical supercomputers now in use and (2) the combustion of typical hydrocarbons proceeds through decomposition into hundreds of molecular species interacting through thousands of reactions. Hence, the combination of detailed reaction- rate models with the fundamental flow equations yields flow models that are computationally prohibitive. Hence, further, a reduction of at least an order of magnitude in the dimension of reaction kinetics is one of the prerequisites for feasibility of computational simulation of turbulent, chemically reacting flows. In the present method of simplified modeling, all molecular species involved in the oxidation of hydrocarbons are classified as either light or heavy; heavy molecules are those having 3 or more carbon atoms. The light molecules are not subject to meaningful decomposition, and the heavy molecules are considered to decompose into only 13 specified constituent radicals, a few of which are listed in the table. One constructs a reduced-order model, suitable for use in estimating the release of heat and the evolution of temperature in combustion, from a base comprising the 13 constituent radicals plus a total of 26 other species that include the light molecules and related light free radicals. Then rather than following all possible species through their reaction coordinates, one follows only the reduced set of reaction coordinates of the base. The behavior of the base was examined in test computational simulations of the combustion of heptane in a stirred reactor at various initial pressures ranging from 0.1 to 6 MPa. Most of the simulations were performed for stoichiometric mixtures; some were performed for fuel/oxygen mole ratios of 1/2 and 2.

Bellan, Josette↗
NASA NTRS2021

Constraints on Triple Oxygen Isotope Kinetics

Isotopic disequilibrium is not as well constrained as equilibrium, hindering interpretation of isotopic variations. Kinetic isotope effects, a subset of disequilibrium, are common in nature and have been assumed to be distinct from equilibrium and mass independent isotope effects based on underdeveloped criteria. Using basic physical principles, we provide needed mechanistic constraints on mass-dependent kinetic isotope effects for the triple oxygen isotope system. We find some kinetic isotope effects yield large isotopic variations, exceeding equilibrium, which could be mistaken for mass independent relationships. Meanwhile, other kinetic isotope effects are found to have triple oxygen isotope relationships that could be mistaken for equilibrium isotope effects. Comparison against prior case studies of thermal decomposition of calcite (CaCO3) and brucite (Mg(OH)2) further tests our results. Although oxygen is the focus here, our approach applies to any system with more than two isotopes.

Isotope Geochemistry↗