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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 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
NASA NTRS1994

Kinetic Study of Methyl Acetate Oxidation in a Pt/Al2O3 Fixed-Bed Reactor

To support technology development for future long-term missions, a metabolic simulator will be used in a closed chamber to test the functions of a Controlled Ecological Life Support System (CELSS). Methyl acetate (MA) was selected as the fuel because its metabolic respiratory quotient is near that of humans. A kinetic study of the catalytic oxidation of MA over Pt/Al203 was then conducted to support the design and operation of the simulator. Kinetic data were obtained as a conversion percentage of MA versus retention time. The reaction was studied at one atmosphere and temperatures from 220 to 340 deg. C. The inlet MA concentration was varied from 100 to 2000 ppm with retention times from 0.01 to 10 sec. A first-order rate law and a Langmuir-Hinshelwood rate equation were tested by nonlinear regression of the kinetic data to estimate rate constants in the rate law. Regression results of the L-H equation explain the kinetic data better than the results of the first-order rate law. A Taguchi experimental design was used to study the effects of temperature, retention time, and concentrations of MA, CO2, and O2 on the conversion of MA. Results indicate that temperature has greatest effect, followed by retention time, and finally MA concentration. It was further determined that the effects of CO2 and O2 concentrations, and the cross effects, are negligible.

Hoy, Michael↗
NASA NTRS1996

Metastable Solution Thermodynamic Properties and Crystal Growth Kinetics

The crystal growth rates of NH4H2PO4, KH2PO4, (NH4)2SO4, KAl(SO4)2 central dot 12H2O, NaCl, and glycine and the nucleation rates of KBr, KCl, NaBr central dot 2H2O, (NH4)2Cl, and (NH4)2SO4 were expressed in terms of the fundamental driving force of crystallization calculated from the activity of supersaturated solutions. The kinetic parameters were compared with those from the commonly used kinetic expression based on the concentration difference. From the viewpoint of thermodynamics, rate expressions based on the chemical potential difference provide accurate kinetic representation over a broad range of supersaturation. The rates estimated using the expression based on the concentration difference coincide with the true rates of crystallization only in the concentration range of low supersaturation and deviate from the true kinetics as the supersaturation increases.

Kim, Soojin↗
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 NTRS1998

A Gas-Kinetic Scheme for Reactive Flows

In this paper, the gas-kinetic BGK scheme for the compressible flow equations is extended to chemical reactive flow. The mass fraction of the unburnt gas is implemented into the gas kinetic equation by assigning a new internal degree of freedom to the particle distribution function. The new variable can be also used to describe fluid trajectory for the nonreactive flows. Due to the gas-kinetic BGK model, the current scheme basically solves the Navier-Stokes chemical reactive flow equations. Numerical tests validate the accuracy and robustness of the current kinetic method.

Lian,Youg-Sheng↗
NASA NTRS1998

Time-Resolved O3 Chemical Chain Reaction Kinetics Via High-Resolution IR Laser Absorption Methods

Excimer laser photolysis in combination with time-resolved IR laser absorption detection of OH radicals has been used to study O3/OH(v = 0)/HO2 chain reaction kinetics at 298 K, (i.e.,(k(sub 1) is OH + 03 yields H02 + 02 and (k(sub 2) is H02 + 03 yields OH + 202). From time-resolved detection of OH radicals with high-resolution near IR laser absorption methods, the chain induction kinetics have been measured at up to an order of magnitude higher ozone concentrations ([03] less than or equal to 10(exp 17) molecules/cu cm) than accessible in previous studies. This greater dynamic range permits the full evolution of the chain induction, propagation, and termination process to be temporally isolated and measured in real time. An exact solution for time-dependent OH evolution under pseudo- first-order chain reaction conditions is presented, which correctly predicts new kinetic signatures not included in previous OH + 03 kinetic analyses. Specifically, the solutions predict an initial exponential loss (chain "induction") of the OH radical to a steady-state level ([OH](sub ss)), with this fast initial decay determined by the sum of both chain rate constants, k(sub ind) = k(sub 1) + k(sub 2). By monitoring the chain induction feature, this sum of the rate constants is determined to be k(sub ind) = 8.4(8) x 10(exp -14) cu cm/molecule/s for room temperature reagents. This is significantly higher than the values currently recommended for use in atmospheric models, but in excellent agreement with previous results from Ravishankara et al.

Kulcke, Axel↗
NASA NTRS1999

Oxygen Diffusion and Reaction Kinetics in Continuous Fiber Ceramic Matrix Composites

Previous stressed oxidation tests of C/SiC composites at elevated temperatures (350 C to 1500 C) and sustained stresses (69 MPa and 172 MPa) have led to the development of a finite difference cracked matrix model. The times to failure in the samples suggest oxidation occurred in two kinetic regimes defined by the rate controlling mechanisms (i.e. diffusion controlled and reaction controlled kinetics). Microstructural analysis revealed preferential oxidation along as-fabricated, matrix microcracks and also suggested two regimes of oxidation kinetics dependent on the oxidation temperature. Based on experimental results, observation, and theory, a finite difference model was developed. The model simulates the diffusion of oxygen into a matrix crack bridged by carbon fibers. The model facilitates the study of the relative importance of temperature, the reaction rate constant, and the diffusion coefficient on the overall oxidation kinetics.

Halbig, Michael C.↗
NASA NTRS1996

Nonlinear Response of Layer Growth Dynamics in the Mixed Kinetics-Bulk-Transport Regime

In situ high-resolution interferometry on horizontal facets of the protein lysozyme reveal that the local growth rate R, vicinal slope p, and tangential (step) velocity v fluctuate by up to 80% of their average values. The time scale of these fluctuations, which occur under steady bulk transport conditions through the formation and decay of step bunches (macrosteps), is of the order of 10 min. The fluctuation amplitude of R increases with growth rate (supersaturation) and crystal size, while the amplitude of the v and p fluctuations changes relatively little. Based on a stability analysis for equidistant step trains in the mixed transport-interface-kinetics regime, we argue that the fluctuations originate from the coupling of bulk transport with nonlinear interface kinetics. Furthermore, step bunches moving across the interface in the direction of or opposite to the buoyancy-driven convective flow increase or decrease in height, respectively. This is in agreement with analytical treatments of the interaction of moving steps with solution flow. Major excursions in growth rate are associated with the formation of lattice defects (striations). We show that, in general, the system-dependent kinetic Peclet number, Pe(sub k) , i.e., the relative weight of bulk transport and interface kinetics in the control of the growth process, governs the step bunching dynamics. Since Pe(sub k) can be modified by either forced solution flow or suppression of buoyancy-driven convection under reduced gravity, this model provides a rationale for the choice of specific transport conditions to minimize the formation of compositional inhomogeneities under steady bulk nutrient crystallization conditions.

Vekilov, Peter G.↗
NASA NTRS1999

A Gas-Kinetic Scheme for Multimaterial Flows and Its Application in Chemical Reaction

This paper concerns the extension of the multicomponent gas-kinetic BGK-type scheme to multidimensional chemical reactive flow calculations. In the kinetic model, each component satisfies its individual gas-kinetic BGK equation and the equilibrium states of both components are coupled in space and time due to the momentum and energy exchange in the course of particle collisions. At the same time, according to the chemical reaction rule one component can be changed into another component with the release of energy, where the reactant and product could have different gamma. Many numerical test cases are included in this paper, which show the robustness and accuracy of kinetic approach in the description of multicomponent reactive flows.

Lian, Yongsheng↗
NASA NTRS2001

Measurement of the Turbulence Kinetic Energy Budget of a Turbulent Planar Wake Flow in Pressure Gradients

Turbulence kinetic energy (TKE) is a very important quantity for turbulence modeling and the budget of this quantity in its transport equation can provide insight into the flow physics. Turbulence kinetic energy budget measurements were conducted for a symmetric turbulent wake flow subjected to constant zero, favorable and adverse pressure gradients in year-three of research effort. The purpose of this study is to clarify the flow physics issues underlying the demonstrated influence of pressure gradient on wake development and provide experimental support for turbulence modeling. To ensure the reliability of these notoriously difficult measurements, the experimental procedure was carefully designed on the basis of an uncertainty analysis. Four different approaches, based on an isotropic turbulence assumption, a locally axisymmetric homogeneous turbulence assumption, a semi-isotropy assumption and a forced balance of the TKE equation, were applied for the estimate of the dissipation term. The pressure transport term is obtained from a forced balance of the turbulence kinetic energy equation. This report will present the results of the turbulence kinetic energy budget measurement and discuss their implication on the development of strained turbulent wakes.

Liu, Xiao-Feng↗
NASA NTRS1994

LSENS, A General Chemical Kinetics and Sensitivity Analysis Code for Homogeneous Gas-Phase Reactions: Code Description and Usage - Part 2

LSENS, the Lewis General Chemical Kinetics and Sensitivity Analysis Code, has been developed for solving complex, homogeneous, gas-phase chemical kinetics problems and contains sensitivity analysis for a variety of problems, including nonisothermal situations. This report is part II of a series of three reference publications that describe LSENS, provide a detailed guide to its usage, and present many example problems. Part II describes the code, how to modify it, and its usage, including preparation of the problem data file required to execute LSENS. Code usage is illustrated by several example problems, which further explain preparation of the problem data file and show how to obtain desired accuracy in the computed results. LSENS is a flexible, convenient, accurate, and efficient solver for chemical reaction problems such as static system; steady, one-dimensional, inviscid flow; reaction behind incident shock wave, including boundary layer correction; and perfectly stirred (highly backmixed) reactor. In addition, the chemical equilibrium state can be computed for the following assigned states: temperature and pressure, enthalpy and pressure, temperature and volume, and internal energy and volume. For static problems the code computes the sensitivity coefficients of the dependent variables and their temporal derivatives with respect to the initial values of the dependent variables and/or the three rate coefficient parameters of the chemical reactions. Part I (NASA RP-1328) derives the governing equations and describes the numerical solution procedures for the types of problems that can be solved by LSENS. Part III (NASA RP-1330) explains the kinetics and kinetics-plus-sensitivity-analysis problems supplied with LSENS and presents sample results.

Radhakrishnan, Krishnan↗
NASA NTRS2003

Kinetics of Organic Transformations Under Mild Aqueous Conditions: Implications for the Origin of Life and Its Metabolism

The rates of thermal transformation of organic molecules containing carbon, hydrogen, and oxygen were systematically examined in order to identify the kinetic constraints that governed origin-of-life organic chemistry under mild aqueous conditions. Arrhenius plots of the kinetic data were used to estimate the reaction half-life at 50 C, and to reveal the effect of functional groups on reactivity. This survey showed that hydrocarbons and organic substances containing a single oxygenated group were kinetically the most stable (i. e. acetate decarboxylation half-life was l0(exp 18) years at 50 C); whereas, organic substances containing two oxygenated groups in which one group was a beta-positioned carbonyl group were the most reactive (i. e. acetoacetate decarboxylation half-life was l0(exp-2) years at 50 C). Of all functional groups the beta-positioned carbonyl group (aldehyde or ketone) was the strongest activating group, giving rates of reaction that were up to 10(exp 24)-times faster than rates of similar molecules lacking the beta-carbonyl group. From this knowledge of organic reactivity and the inherent constraints of autocatalytic processes, we concluded that an origins-of-life process based on autocatalytic transformation of C,H,O-substrates was constrained to using the most reactive organic molecules that contain alpha- or beta-carbonyl groups, since small autocatalytic domains of plausible catalytic power that used less reactive substrates could not carry out chemical transformations fast enough to prevent catastrophic efflux (escape) of reaction intermediates. Knowledge of the kinetics of organic transformations is useful, not only in constraining the chemistry of the earliest autocatalytic process related to the origin of life, but also in establishing the relative reactivity of organic molecules on the early Earth and other planets that may or may not be related to the origin of life.

Weber, Arthur L.↗
NASA NTRS1992

Comparative kinetics and reciprocal inhibition of nitrate and nitrite uptake in roots of uninduced and induced barley (Hordeum vulgare L.) seedlings

Nitrate and NO2- transport by roots of 8-day-old uninduced and induced intact barley (Hordeum vulgare L. var CM 72) seedlings were compared to kinetic patterns, reciprocal inhibition of the transport systems, and the effect of the inhibitor, p-hydroxymercuribenzoate. Net uptake of NO3- and NO2- was measured by following the depletion of the ions from the uptake solutions. The roots of uninduced seedlings possessed a low concentration, saturable, low Km, possibly a constitutive uptake system, and a linear system for both NO3- and NO2-. The low Km system followed Michaelis-Menten kinetics and approached saturation between 40 and 100 micromolar, whereas the linear system was detected between 100 and 500 micromolar. In roots of induced seedlings, rates for both NO3- and NO2- uptake followed Michaelis-Menten kinetics and approached saturation at about 200 micromolar. In induced roots, two kinetically identifiable transport systems were resolved for each anion. At the lower substrate concentrations, less than 10 micromolar, the apparent low Kms of NO3- and NO2- uptake were 7 and 9 micromolar, respectively, and were similar to those of the low Km system in uninduced roots. At substrate concentrations between 10 and 200 micromolar, the apparent high Km values of NO3- uptake ranged from 34 to 36 micromolar and of NO2- uptake ranged from 41 to 49 micromolar. A linear system was also found in induced seedlings at concentrations above 500 micromolar. Double reciprocal plots indicated that NO3- and NO2- inhibited the uptake of each other competitively in both uninduced and induced seedlings; however, Ki values showed that NO3- was a more effective inhibitor than NO2-. Nitrate and NO2- transport by both the low and high Km systems were greatly inhibited by p-hydroxymercuribenzoate, whereas the linear system was only slightly inhibited.

NASA Program CELSS↗
NASA NTRS1996

Calcium kinetics with microgram stable isotope doses and saliva sampling

Studies of calcium kinetics require administration of tracer doses of calcium and subsequent repeated sampling of biological fluids. This study was designed to develop techniques that would allow estimation of calcium kinetics by using small (micrograms) doses of isotopes instead of the more common large (mg) doses to minimize tracer perturbation of the system and reduce cost, and to explore the use of saliva sampling as an alternative to blood sampling. Subjects received an oral dose (133 micrograms) of 43Ca and an i.v. dose (7.7 micrograms) of 46Ca. Isotopic enrichment in blood, urine, saliva and feces was well above thermal ionization mass spectrometry measurement precision up to 170 h after dosing. Fractional calcium absorptions determined from isotopic ratios in blood, urine and saliva were similar. Compartmental modeling revealed that kinetic parameters determined from serum or saliva data were similar, decreasing the necessity for blood samples. It is concluded from these results that calcium kinetics can be assessed with micrograms doses of stable isotopes, thereby reducing tracer costs and with saliva samples, thereby reducing the amount of blood needed.

Clinical Trial↗
NASA NTRS2002

Comparison of the Effects of Wave-Particle Interactions and the Kinetic Suprathermal Electron Population on the Acceleration of the Solar Wind

Kinetic effects due to wave-particle interactions and suprathermal electrons have been suggested in the literature as possible solar wind acceleration mechanisms. Ion cyclotron resonant heating, in particular, has been associated with some qualitative features observed in the solar wind. In terms of solar wind acceleration, however, it is interesting to compare the kinetic effects of suprathermal electrons with those due to the wave-particle interactions. The combined effects of the two acceleration mechanisms on the fast solar wind have been studied by Tam and Chang (1999a,b). In this study. we investigate the role of the suprathermal electron population in the acceleration of the solar wind. Our model follows the global kinetic evolution of the fast solar wind under the influence of ion cyclotron resonant heating, while taking into account Coulomb collisions, and the ambipolar electric field that is consistent with the particle distributions themselves. The kinetic effects due to the suprathermal electrons, which we define to be the tail of the electron distributions, can be included in the model as an option. By comparing the results with and without the inclusion of the suprathermal electron effects, we determine the relative importance of suprathermal electrons and wave-particle interactions in driving the solar wind. We find that although suprathermal electrons enhance the ambipolar electric potential in the solar wind considerably, their overall influence as an acceleration mechanism is relatively insignificant in a wave-driven solar wind.

Tam, S. W. Y.↗
NASA NTRS2006

Determining Kinetic Parameters for Isothermal Crystallization of Glasses

Non-isothermal crystallization techniques are frequently used to determine the kinetic parameters for crystallization in glasses. These techniques are experimentally simple and quick compared to the isothermal techniques. However, the analytical models used for non-isothermal data analysis, originally developed for describing isothermal transformation kinetics, are fundamentally flawed. The present paper describes a technique for determining the kinetic parameters for isothermal crystallization in glasses, which eliminates most of the common problems that generally make the studies of isothermal crystallization laborious and time consuming. In this technique, the volume fraction of glass that is crystallized as a function of time during an isothermal hold was determined using differential thermal analysis (DTA). The crystallization parameters for the lithium-disilicate (Li2O.2SiO2) model glass were first determined and compared to the same parameters determined by other techniques to establish the accuracy and usefulness of the present technique. This technique was then used to describe the crystallization kinetics of a complex Ca-Sr-Zn-silicate glass developed for sealing solid oxide fuel cells.

Ray, C. S.↗
NASA NTRS2008

Kinetic Temperature and Electron Density Measurement in an Inductively Coupled Plasma Torch using Degenerate Four-Wave Mixing

Laser wave mixing is presented as an effective technique for spatially resolved kinetic temperature measurements in an atmospheric-pressure radio-frequency inductively-coupled plasma. Measurements are performed in a 1 kW, 27 MHz RF plasma using a continuous-wave, tunable 811.5-nm diode laser to excite the 4s(sup 3)P2 approaches 4p(sup 3)D3 argon transition. Kinetic temperature measurements are made at five radial steps from the center of the torch and at four different torch heights. The kinetic temperature is determined by measuring simultaneously the line shape of the sub-Doppler backward phase-conjugate degenerate four-wave mixing and the Doppler-broadened forward-scattering degenerate four-wave mixing. The temperature measurements result in a range of 3,500 to 14,000 K+/-150 K. Electron densities measured range from 6.1 (+/-0.3) x 10(exp 15)/cu cm to 10.1 (+/-0.3) x 10(exp 15)/cu cm. The experimental spectra are analyzed using a perturbative treatment of the backward phase-conjugate and forward-geometry wave-mixing theory. Stark width is determined from the collisional broadening measured in the phase-conjugate geometry. Electron density measurements are made based on the Stark width. The kinetic temperature of the plasma was found to be more than halved by adding deionized water through the nebulizer.

Schafer, Julia↗
NASA NTRS2017

Evaluation of the Uncertainty in JP-7 Kinetics Models Applied to Scramjets

One of the challenges of designing and flying a scramjet-powered vehicle is the difficulty of preflight testing. Ground tests at realistic flight conditions introduce several sources of uncertainty to the flow that must be addressed. For example, the scales of the available facilities limit the size of vehicles that can be tested and so performance metrics for larger flight vehicles must be extrapolated from ground tests at smaller scales. To create the correct flow enthalpy for higher Mach number flows, most tunnels use a heater that introduces vitiates into the flow. At these conditions, the effects of the vitiates on the combustion process is of particular interest to the engine designer, where the ground test results must be extrapolated to flight conditions. In this paper, the uncertainty of the cracked JP-7 chemical kinetics used in the modeling of a hydrocarbon-fueled scramjet was investigated. The factors that were identified as contributing to uncertainty in the combustion process were the level of flow vitiation, the uncertainty of the kinetic model coefficients and the variation of flow properties between ground testing and flight. The method employed was to run simulations of small, unit problems and identify which variables were the principal sources of uncertainty for the mixture temperature. Then using this resulting subset of all the variables, the effects of the uncertainty caused by the chemical kinetics on a representative scramjet flow-path for both vitiated (ground) and nonvitiated (flight) flows were investigated. The simulations showed that only a few of the kinetic rate equations contribute to the uncertainty in the unit problem results, and when applied to the representative scramjet flowpath, the resulting temperature variability was on the order of 100 K. Both the vitiated and clean air results showed very similar levels of uncertainty, and the difference between the mean properties were generally within the range of uncertainty predicted.

Norris, A. T.↗
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↗