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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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All sourcesNASA NTRSDOE OSTI
NASA NTRS1984

A comparison of the efficiency of numerical methods for integrating chemical kinetic rate equations

A comparison of the efficiency of several algorithms recently developed for the efficient numerical integration of stiff ordinary differential equations is presented. The methods examined include two general-purpose codes EPISODE and LSODE and three codes (CHEMEQ, CREK1D, and GCKP84) developed specifically to integrate chemical kinetic rate equations. The codes are applied to two test problems drawn from combustion kinetics. The comparisons show that LSODE is the fastest code currently available for the integration of combustion kinetic rate equations. An important finding is that an iterative solution of the algebraic energy conservation equation to compute the temperature can be more efficient than evaluating the temperature by integrating its time-derivative.

Radhakrishnan, K.↗
NASA NTRS1985

Shock tube study of the fuel structure effects on the chemical kinetic mechanisms responsible for soot formation, part 2

Soot formation in oxidation of allene, 1,3-butadiene, vinylacetylene and chlorobenzene and in pyrolysis of ethylene, vinylacetylene, 1-butene, chlorobenzene, acetylen-hydrogen, benzene-acetylene, benzene-butadiene and chlorobenzene-acetylene argon-diluted mixtures was studied behind reflected shock waves. The results are rationalized within the framework of the conceptual models. It is shown that vinylacetylene is much less sooty than allene, which indicates that conjugation by itself is not a sufficient factor for determining the sooting tendency of a molecule. Structural reactivity in the context of the chemical kinetics is the dominant factor in soot formation. Detailed chemical kinetic modeling of soot formation in pyrolysis of acetylene is reported. The main mass growth was found to proceed through a single dominant route composed of conventional radical reactions. The practically irreversible formation reactions of the fused polycyclic aromatics and the overshoot by hydrogen atom over its equilibrium concentration are the g-driving kinetic forces for soot formation.

Frenklach, M.↗
NASA NTRS1985

Integrating chemical kinetic rate equations by selective use of stiff and nonstiff methods

The effect of switching between nonstiff and stiff methods on the efficiency of algorithms for integrating chemical kinetic rate equations is presented. Different integration methods are tested by application of the packaged code LSODE to four practical combustion kinetics problems. The problems describe adiabatic, homogeneous gas-phase combustion reactions. It is shown that selective use of nonstiff and stiff methods in different regimes of a typical batch combustion problem is faster than the use of either method for the entire problem. The implications of this result to the development of fast integration techniques for combustion kinetic rate equations are discussed.

Radhakrishnan, K.↗
NASA NTRS1984

A kinetic energy analysis of the meso beta-scale severe storm environment

Analyses are performed of the meso beta-scale (20-200 km wavelengths and several hours to one-day periods) severe storm kinetic energy balance on the fifth day of the AVE SESAME campaign of May 1979. A 24-hr interval covering the antecedent, active and post-convective outbreak activity over Oklahoma are considered. Use is made of the kinetic energy budget equation (KEBE) for a finite volume in an isobaric coordinate system. Rawindsonde data with 75 km resolution were treated. The KEBE model covered changes in kinetic energy due to the cross contour flows, horizontal and vertical components of flux divergence, and volumic mass changes on synoptic and subsynoptic scales. The greatest variability was concentrated above 400 mb height and over the most intense storm activity. Energy was generated at the highest rates in divergence and decreased the most in convection. The meso beta-scale lacked sufficient resolution for analyzing mesoscale activity.

Fuelberg, H. E.↗
NASA NTRS1985

Colloidal Oxide Properties and Kinetic Studies

Silica based oxide particles prepared by various methods are compared in terms of their gellation kinetics, densification kinetics, and microable structural evolutions begin at very low temperature. Additional work reported in literature further suggested that the colloidal behaviors and the dried gel structures of the same oxide from different preparation techniques differ fundamentally. These differences significantly affect the densification kinetics and the product microstructure. Gravitational segregation of particles of different sizes in a gravitational field is modelled as a diffusion/segregation problem. A structural free volume model was used to describe the activation process of jump statistics. The sizes of the particles, the interstices, and their packing topology are accounted for in the estimation of the free volume. An attempt frequency is ascribed to particles to account for the vibrational rearrangement during powder packing.

Chen, I. W.↗
NASA NTRS1986

Group-kinetic theory of turbulence

The two phases are governed by two coupled systems of Navier-Stokes equations. The couplings are nonlinear. These equations describe the microdynamical state of turbulence, and are transformed into a master equation. By scaling, a kinetic hierarchy is generated in the form of groups, representing the spectral evolution, the diffusivity and the relaxation. The loss of memory in formulating the relaxation yields the closure. The network of sub-distributions that participates in the relaxation is simulated by a self-consistent porous medium, so that the average effect on the diffusivity is to make it approach equilibrium. The kinetic equation of turbulence is derived. The method of moments reverts it to the continuum. The equation of spectral evolution is obtained and the transport properties are calculated. In inertia turbulence, the Kolmogoroff law for weak coupling and the spectrum for the strong coupling are found. As the fluid analog, the nonlinear Schrodinger equation has a driving force in the form of emission of solitons by velocity fluctuations, and is used to describe the microdynamical state of turbulence. In order for the emission together with the modulation to participate in the transport processes, the non-homogeneous Schrodinger equation is transformed into a homogeneous master equation. By group-scaling, the master equation is decomposed into a system of transport equations, replacing the Bogoliubov system of equations of many-particle distributions. It is in the relaxation that the memory is lost when the ensemble of higher-order distributions is simulated by an effective porous medium. The closure is thus found. The kinetic equation is derived and transformed into the equation of spectral flow.

Tchen, C. M.↗
NASA NTRS1986

Fast algorithm for calculating chemical kinetics in turbulent reacting flow

This paper addresses the need for a fast batch chemistry solver to perform the kinetics part of a split operator formulation of turbulent reacting flows, with special attention focused on the solution of the ordinary differential equations governing a homogeneous gas-phase chemical reaction. For this purpose, a two-part predictor-corrector algorithm which incorporates an exponentially fitted trapezoidal method was developed. The algorithm performs filtering of ill-posed initial conditions, automatic step-size selection, and automatic selection of Jacobi-Newton or Newton-Raphson iteration for convergence to achieve maximum computational efficiency while observing a prescribed error tolerance. The new algorithm, termed CREK1D (combustion reaction kinetics, one-dimensional), compared favorably with the code LSODE when tested on two representative problems drawn from combustion kinetics, and is faster than LSODE.

Radhakrishnan, K.↗
NASA NTRS1988

Initial conditions implied by t exp 1/2 solidification of a sphere with capillarity and interfacial kinetics

The paper explores the initial conditions implied by t exp 1/2 growth of a spherical crystal solidifying from a pure, undercooled melt, including the effects of both capillarity and interface kinetics, and relates the findings to initial conditions that would be expected on the basis of classical nucleation theory. For crystal sizes near the nucleation radius, the calculated temperature profiles show a cold region ahead of the advancing interface that is even more undercooled than the undercooled bath. This cold region acts as a local heat sink that compensates for the reduced growth speed that would otherwise result from capillarity and kinetics, leading to precisely the same t exp 1/2 growth law that would have been obtained had both capillarity and kinetics been neglected.

Sekerka, R. F.↗
NASA NTRS1988

The effect of Co alloying content on the kinetics of reaction zone growth in tungsten fiber reinforced superalloy composites

A Co-free modified superalloy similar in composition to Waspaloy is investigated in an effort to understand the effect of Co on reaction zone growth kinetics and verify the chemistry dependence of reaction zone growth in the matrix of tungsten fiber reinforced superalloy composites. The values of the parabolic rate constant, characterizing the kinetics of reaction zone growth, for the Waspaloy matrix and the C-free alloy as well as five other alloys from a previous study confirm the dependence of reaction zone growth kinetics on cobalt content of the matrix. The Co-free alloy composite exhibits the slowest reaction zone growth among all tungsten fiber reinforced composites studied to date.

Rodriguez, A.↗
NASA NTRS1989

Turbulence kinetic energy equation for dilute suspensions

A multiphase turbulence closure model is presented which employs one transport equation, namely the turbulence kinetic energy equation. The proposed form of this equation is different from the earlier formulations in some aspects. The power spectrum of the carrier fluid is divided into two regions, which interact in different ways and at different rates with the suspended particles as a function of the particle-eddy size ratio and density ratio. The length scale is described algebraically. A mass/time averaging procedure for the momentum and kinetic energy equations is adopted. The resulting turbulence correlations are modeled under less retrictive assumptions comparative to previous work. The closures for the momentum and kinetic energy equations are given. Comparisons of the predictions with experimental results on liquid-solid jet and gas-solid pipe flow show satisfactory agreement.

Abou-Arab, T. W.↗
NASA NTRS1990

Chemical kinetics and modeling of planetary atmospheres

A unified overview is presented for chemical kinetics and chemical modeling in planetary atmospheres. The recent major advances in the understanding of the chemistry of the terrestrial atmosphere make the study of planets more interesting and relevant. A deeper understanding suggests that the important chemical cycles have a universal character that connects the different planets and ultimately link together the origin and evolution of the solar system. The completeness (or incompleteness) of the data base for chemical kinetics in planetary atmospheres will always be judged by comparison with that for the terrestrial atmosphere. In the latter case, the chemistry of H, O, N, and Cl species is well understood. S chemistry is poorly understood. In the atmospheres of Jovian planets and Titan, the C-H chemistry of simple species (containing 2 or less C atoms) is fairly well understood. The chemistry of higher hydrocarbons and the C-N, P-N chemistry is much less understood. In the atmosphere of Venus, the dominant chemistry is that of chlorine and sulfur, and very little is known about C1-S coupled chemistry. A new frontier for chemical kinetics both in the Earth and planetary atmospheres is the study of heterogeneous reactions. The formation of the ozone hole on Earth, the ubiquitous photochemical haze on Venus and in the Jovian planets and Titan all testify to the importance of heterogeneous reactions. It remains a challenge to connect the gas phase chemistry to the production of aerosols.

Yung, Yuk L.↗
NASA NTRS1990

The applications of chemical thermodynamics and chemical kinetics to planetary atmospheres research

A review of the applications of chemical thermodynamics and chemical kinetics to planetary atmospheres research during the past four decades is presented with an emphasis on chemical equilibrium models and thermochemical kinetics. Several current problems in planetary atmospheres research such as the origin of the atmospheres of the terrestrial planets, atmosphere-surface interactions on Venus and Mars, deep mixing in the atmospheres of the gas giant planets, and the origin of the atmospheres of outer planet satellites all require laboratory data on the kinetics of thermochemical reactions for their solution.

Fegley, Bruce, Jr.↗
NASA NTRS1990

An in situ X ray diffraction study of the kinetics of the Ni2SiO4 olivine-spinel transformation

The kinetics of the olivine-spinel transformation in Ni2SiO4 were investigated in an in situ X-ray diffraction experiments in which synchrotron radiation was used as an X-ray source. The starting material was Ni2SO4 olivine which was hot-pressed in situ at 980 C and 2.5 GPa; during the transformation, X-ray diffraction patterns were collected at intervals of 30 or 120 sec. The kinetic data were analyzed using Cahn's (1956) model. The activation energy for growth at 3.6-3.7 GPa was estimated as 438 + or - 199 kJ/mol. It is shown that, in order to make significant extrapolations of the kinetic data to a geological scale, the dependence of the rates of both nucleation and growth on temperature and pressure must be evaluated separately.

Rubie, D. C.↗
NASA NTRS1991

Kinetics of volatile extraction from carbonaceous chondrites: Dehydration of talc

Carbonaceous chondrites are believed to be the primary constituents of near-Earth asteroids and Phobos and Deimos, and are potential resources of fuels that may be exploited for future planetary missions. Calculations of equilibrium phase relations suggest that talc (Ta) and antigorite (Ant) are likely to be the major hydrous phases in the C1 and C2 meteorites (Ganguly and Saxena, 1989), which constitute the most volatile rich classes of carbonaceous chondrites. The dehydration kinetics of talc are studied as a function of temperature, grain size, composition and fluid fugacity, as part of a systematic study of the reaction kinetics of the volatile bearing phases that are either known or likely to be present in carbonaceous chondrites. The dehydration kinetics were investigated at 1 bar, 775 to 875 C by monitoring the in-situ weight loss as a function of time of a natural talc. The talc platelets had a dimension of 0.8 to 1 micron. The run durations varied from 233.3 hours at 775 C (48 percent dehydration) to 20.8 hours at 875 C (80 pct. dehydration). The results can be adequately represented by a given rate equation. Theoretical analysis suggests that the reduction in the concentration of H2O in the environment of dehydrating talc, as would be encountered in processing chondritic materials, will have negligible effect on the rate of dehydration, unless there is a change of reaction mechanism owing to the presence of other volatile species.

Bose, Kunal↗
NASA NTRS1992

Global Kinetic Constants for Thermal Oxidative Degradation of a Cellulosic Paper

Values of global kinetic constants for pyrolysis, thermal oxidative degradation, and char oxidation of a cellulosic paper were determined by a derivative thermal gravimetric study. The study was conducted at heating rates of 0.5, 1, 1.5, 3, and 5 C/min in ambient atmospheres of nitrogen, 0.28, 1.08, 5.2 percent oxygen concentrations, and air. Sample weight loss rate, concentrations of CO, CO2, and H2O in the degradation products, and oxygen consumption were continuously measured during the experiment. Values of activation energy, preexponential factor, orders of reaction, and yields of CO, CO2, H2O, total hydrocarbons, and char for each degradation reaction were derived from the results. Heat of reaction for each reaction was determined by differential scanning calorimetry. A comparison of the calculated CO, CO2, H2O, total hydrocarbons, sample weight loss rate, and oxygen consumption was made with the measured results using the derived kinetic constants, and the accuracy of the values of kinetic constants was discussed.

Kashiwagi, Takashi↗
NASA NTRS1992

The platinum microelectrode/Nafion interface - An electrochemical impedance spectroscopic analysis of oxygen reduction kinetics and Nafion characteristics

The objectives of this study were to use electrochemical impedance spectroscopy (EIS) to study the oxygen-reduction reaction under lower humidification conditions than previously studied. The EIS technique permits the discrimination of electrode kinetics of oxygen reduction, mass transport of O2 in the membrane, and the electrical characteristics of the membrane. Electrode-kinetic parameters for the oxygen-reduction reaction, corrosion current densities for Pt, and double-layer capacitances were calculated. The production of water due to electrochemical reduction of oxygen greatly influenced the EIS response and the electrode kinetics at the Pt/Nafion interface. From the finite-length Warburg behavior, a measure of the diffusion coefficient of oxygen in Nafion and diffusion-layer thickness was obtained. An analysis of the EIS data in the high-frequency domain yielded membrane and interfacial characteristics such as ionic conductivity of the membrane, membrane grain-boundary capacitance and resistance, and uncompensated resistance.

Parthasarathy, Arvind↗
NASA NTRS1993

A critical analysis of the accuracy of several numerical techniques for combustion kinetic rate equations

A detailed analysis of the accuracy of several techniques recently developed for integrating stiff ordinary differential equations is presented. The techniques include two general-purpose codes EPISODE and LSODE developed for an arbitrary system of ordinary differential equations, and three specialized codes CHEMEQ, CREK1D, and GCKP4 developed specifically to solve chemical kinetic rate equations. The accuracy study is made by application of these codes to two practical combustion kinetics problems. Both problems describe adiabatic, homogeneous, gas-phase chemical reactions at constant pressure, and include all three combustion regimes: induction, heat release, and equilibration. To illustrate the error variation in the different combustion regimes the species are divided into three types (reactants, intermediates, and products), and error versus time plots are presented for each species type and the temperature. These plots show that CHEMEQ is the most accurate code during induction and early heat release. During late heat release and equilibration, however, the other codes are more accurate. A single global quantity, a mean integrated root-mean-square error, that measures the average error incurred in solving the complete problem is used to compare the accuracy of the codes. Among the codes examined, LSODE is the most accurate for solving chemical kinetics problems. It is also the most efficient code, in the sense that it requires the least computational work to attain a specified accuracy level. An important finding is that use of the algebraic enthalpy conservation equation to compute the temperature can be more accurate and efficient than integrating the temperature differential equation.

Radhadrishnan, Krishnan↗
NASA NTRS1992

Dehydration kinetics and thermochemistry of selected hydrous phases, and simulated gas release pattern in carbonaceous chondrites

As part of our continued program of study on the volatile bearing phases and volatile resource potential of carbonaceous chondrite, results of our experimental studies on the dehydration kinetics of talc as a function of temperature and grain size (50 to 0.5 microns), equilibrium dehydration boundary of talc to 40 kbars, calorimetric study of enthalpy of formation of both natural and synthetic talc as a function of grain size, and preliminary results on the dehydration kinetics of epsomite are reported. In addition, theoretical calculations on the gas release pattern of Murchison meteorite, which is a C2(CM) carbonaceous chondrite, were performed. The kinetic study of talc leads to a dehydration rate constant for 40-50 microns size fraction of k = (3.23 x 10(exp 4))exp(-Q/RT)/min with the activation energy Q = 376 (plus or minus 20) kJ/mole. The dehydration rate was found to increase somewhat with decreasing grain size. The enthalpy of formation of talc from elements was measured to be -5896(10) kJ/mol. There was no measurable effect of grain size on the enthalpy beyond the limits of precision of the calorimetric studies. Also the calorimetric enthalpy of both synthetic and natural talc was found to be essentially the same, within the precision of measurements, although the natural talc had a slightly larger field of stability in our phase equilibrium studies. The high pressure experimental data the dehydration equilibrium of talc (talc = enstatite + coesite + H2O) is in strong disagreement with that calculated from the available thermochemical data, which were constrained to fit the low pressure experimental results. The calculated gas release pattern of Murchison meteorite were in reasonable agreement with that determined by stepwise heating in a gas chromatograph.

Bose, Kunal↗