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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 361 records · Page 20
All sourcesNASA NTRSDOE OSTI
NASA NTRS1979

Pressure and temperature dependence kinetics study of the NO + BrO yielding NO2 + Br reaction - Implications for stratospheric bromine photochemistry

The reactivity of NO with BrO radicals over a wide range of pressure (100-700 torr) and temperature (224-398 K) is investigated using the flash photolysis-ultraviolet absorption technique. The flash photolysis system consists of a high-pressure xenon arc light source, a reaction cell/gas filter/flash lamp combination, and a 216.5 half-meter monochromator/polychromator/spectrography for wavelength selectivity. The details of the reaction and its corresponding Arrhenius expression are identified. The results are compared with previous measurements, and atmospheric implications of the reaction are discussed. The NO + BrO yielding NO2 + Br reaction is shown to be important in controlling the concentration ratios of BrO/Br and BrO/HBr in the stratosphere, but this reaction does not affect the catalytic efficiency of BrOx in ozone destruction.

Watson, R. T.↗
NASA NTRS1979

The OI/1S/ state - Its quenching by O2 and formation by the dissociative recombination of vibrationally excited O2/+/ ions

The rate coefficient for the quenching of metastable O(1S) atoms by O2 was measured as a function of temperature from 250 to 550 K. The resulting Arrhenius expression correlates well with previous laboratory work. It is suggested that the much larger value of the rate coefficient inferred from an analysis of artificial auroral experiment, Precede, may be explained by overestimation of the contribution of O(1S) production from O2(+) dissociative recombination. The possibility that O(1S) atoms are produced only by the dissociative recombination of vibrationally excited O2(+) ions is examined; such excited ions would not exist in the Precede experiment because of the rapid cooling of the ions by resonant charge transfer processes.

Zipf, E. C.↗
NASA NTRS1979

Completion of the Viking Labeled Release experiment on Mars

The final Labeled Release (LR) cycle on each Viking lander tested a surface sample that had been stored for several months at approximately 10 C prior to the onset of the active sequence. At each lander site, activity was strongly diminished. This thermal sensitivity of the active agent on the surface of Mars is consistent with a biological explanation of the LR experiment. At the end of one of these cycles, the incubation mixture was heated to 50 C to release any radioactive gas trapped in the sample matrix. The results suggest that more than one carbon substrate is involved in the LR reaction on Mars. The thermal data from the stored samples, coupled with data from previous cycles, have formed the basis for evaluation of the thermal decomposition of the Mars active agent. The slope of the resulting Arrhenius plot has been used to test the fit of other flight data and to calculate the activation energy for thermal decomposition of the Mars agent. The results and their interpretation still leave unresolved the question of whether the Mars LR data were generated by biological or chemical activity.

Levin, G. V.↗
NASA NTRS1980

Absolute rate constant of the reaction OH + H2O2 yields HO2 + H2O from 245 to 423 K

The absolute rate constant of the reaction between the hydroxyl radical and hydrogen peroxide was measured by using the discharge-flow resonance fluorescence technique at total pressure between 1 and 4 torr. At 298 K the result is (1.64 + or - 0.32) x 10 to the -12th cu cm/molecule s. The observed rate constant is independent of pressure, surface-to-volume ratio, the addition of vibrational quenchers, and the source of OH. The temperature dependence has also been determined between 245 and 423 K; the resulting Arrhenius expression is k cu cm/molecule s is equal to (2.51 + or - 0.6) x 10 to the -12th exp(-126 + or - 76/T).

Keyser, L. F.↗
NASA NTRS1980

Catalytic recombination of nitrogen and oxygen on high-temperature reusable surface insulation

The energy transfer catalytic recombination coefficient for nitrogen and oxygen recombination on the surface coating of high-temperature reusable surface insulation (HRSI) is inferred from stagnation point heat flux measurements in a high-temperature dissociated arc jet flow. The resulting catalytic recombination coefficients are correlated with an Arrhenius model for convenience, and these expressions may be used to account for catalytic recombination effects in predictions of the heat flux on the HRSI thermal protection system of the Space Shuttle Orbiter during reentry flight. Analysis of stagnation point pressure and total heat balance enthalpy measurements indicates that the arc heater reservoir conditions are not in chemical equilibrium. This is contrary to what is usually assumed for arc jet analysis and indicates the need for suitable diagnostics and analyses, especially when dealing with chemical reaction phenomena such as catalytic recombination heat transfer effects.

Scott, C. D.↗
NASA NTRS1980

Critical analysis of nitramine decomposition data: Activation energies and frequency factors for HMX and RDX decomposition

A summary of a literature review on thermal decomposition of HMX and RDX is presented. The decomposition apparently fits first order kinetics. Recommended values for Arrhenius parameters for HMX and RDX decomposition in the gaseous and liquid phases and for decomposition of RDX in solution in TNT are given. The apparent importance of autocatalysis is pointed out, as are some possible complications that may be encountered in interpreting extending or extrapolating kinetic data for these compounds from measurements carried out below their melting points to the higher temperatures and pressure characteristic of combustion.

Schroeder, M. A.↗
NASA NTRS1981

The effects of organosulfur compounds upon the storage stability of Jet A fuel

This study examined the effect of sulfur-containing compounds on the storage stability of Jet A turbine fuel. It was found that alkyl sulfides and disulfides increased the fuel's stability while all thiols and thiophene derivatives tested decreased fuel stability (increased deposit formation) at temperatures and sulfur concentrations selected. Linear Arrhenius plots of sulfur-spiked fuel samples demonstrated that deposit formation decreased with increased slope for all alkyl sulfides, alkyl disulfides, thiols, and thiophene derivatives. A plot of insoluble deposit vs. concentration of added alkyl sulfide produces a negative slope. It appears that the inhibiting mechanism for alkyl sulfides is a result of the compound's reactivity with intermediate soluble precursors to deposit in the fuel. A method of approximating the relative basicity of weak organosulfur bases was developed via measurement of their resonance chemical shifts in proton NMR. Linear plots of log gm. deposit vs. change in chemical shift (shift differences between sulfur bases neat and complexed with I2) were found for alkyl sulfides and alkyl thiols. This suggests the possibility that increased deposit formation is due to base catalysis with these compound classes.

Heneman, F. C.↗
NASA NTRS1980

Ar-40/Ar-39 dating, Ar diffusion properties, and cooling rate determinations of severely shocked chondrites

The ages of Ar-40/Ar-39 chondrites were computed to be 4.29 to 1.0 Gyr, with degassing times of 0.5 to 1.0 Gyr. The values of the diffusion parameter for Ar in Arrhenius plots show linear relationships which correspond to the degassing of different mineral phases with distinct K/Ca ratios and different average temperatures for Ar release. The experimental values of the diffusion parameter for the high-temperature phase of severely shocked chondrites are 10 to the -7th to 10 to the -5th/s for the shock-heating temperatures in the 950-1200 C range; the inferred reheating temperatures and the fraction of the Ar-40 loss during the reheating event suggest post-shock cooling rates and burial depths of 0.01-0.0001 C/s and 0.5-2m, respectively.

Bogard, D. D.↗
NASA NTRS1981

Temperature dependence of the hydrogen atom abstraction reactions of Cl/+/ and HCl/+/ with H2

Rate constants are reported for the reactions of Cl(+) and HCl(+) with H2 over the temperature range 150-400 K. The Cl(+) reaction has a positive temperature dependence that follows the Arrhenius form k1 = A exp(-169/T). The reaction of HCl(+) has a negative temperature dependence that follows the form k2 = AT to the -0.6 power. The implication of these results for interstellar chemistry is commented on. Schematic potential surfaces for the reactions are suggested.

Cates, R. D.↗
NASA NTRS1981

Kinetics of the gas-phase reaction between hydroxyl and carbonyl sulfide over the temperature range 300-517 K

By use of a discharge-flow resonance-fluorescence method the rate constant for the title reaction has been measured at five temperatures in the range 300-520 K. The Arrhenius expression is k(OH + OCS) = (1.3 + or - 0.3) x 10 to the -12th exp/-(2300 + or - 100)/T/ cu cm/s. Mass spectrometry has been used to detect the product HS and to collect some information about its reactivity. This study has carefully avoided the pitfalls associated with possible photolysis of reactants and complications due to H2S impurity in carbonyl sulfide that may have marred previous studies. This study has confirmed that the rate constant for this reaction is so much lower than the value originally used in computer modeling of the upper and lower atmosphere that conclusions about the relative importance of photolysis of OCS and of the reaction OH + OCS in the stratosphere must now be reassessed. The reaction OH + OCS has little significance for atmospheric chemistry.

Leu, M.-T.↗
NASA NTRS1982

A comprehensive model to determine the effects of temperature and species fluctuations on reaction rates in turbulent reacting flows

The use of probability theory to determine the effects of turbulent fluctuations on reaction rates in turbulent combustion systems is briefly reviewed. Results are presented for the effect of species fluctuations in particular. It is found that turbulent fluctuations of species act to reduce the reaction rates, in contrast with the temperature fluctuations previously determined to increase Arrhenius reaction rate constants. For the temperature fluctuations, a criterion is set forth for determining if, in a given region of a turbulent flow field, the temperature can be expected to exhibit ramp like fluctuations. Using the above results, along with results previously obtained, a model is described for testing the effects of turbulent fluctuations of temperature and species on reaction rates in computer programs dealing with turbulent reacting flows. An alternative model which employs three variable probability density functions (temperature and two species) and is currently being formulated is discussed as well.

Chinitz, W.↗
NASA NTRS1981

Temperature dependence of the self-reaction of CH3O2 radicals

The rate constants for the reaction CH3O2 + CH3O2 yields products (1) were measured in the temperature range from 248 to 417 K, taking into consideration pressures in the range from 60 to 700 torr of N2. The experimental investigation was carried out in a Pyrex flash photolysis system employing ultraviolet absorption detection. Methylperoxy radicals (CH3O2) were produced by the photolysis of Cl2-CH4-O2 mixtures. Rate constants were measured by observing the second-order disappearance of CH3O2 radicals. Plots of 1/(CH3O2 optical density) vs. time were observed to be linear over a concentration change of a factor of 10-50. Results of the kinetic runs at each temperature are summarized in a table, and an Arrhenius plot of the data is shown in a graph.

Sander, S. P.↗
NASA NTRS1981

The effect of temperature fluctuations of reaction rate constants in turbulent reacting flows

Current models of turbulent reacting flows frequently use Arrhenius reaction rate constants obtained from static or laminar flow theory and/or experiments, or from best fits of static, laminar, and turbulent data. By treating the reaction rate constant as a continuous random variable which is temperature-dependent, the present study assesses the effect of turbulent temperature fluctuations on the reaction rate constant. This model requires that a probability density function (PDF) describing the nature of the fluctuations be specified. Three PDFs are examined: the clipped Gaussian, the beta PDF, and the ramp model. All the models indicate that the reaction rate constant is greater in a turbulent flow field than in an equivalent laminar flow. In addition, an amplification ratio, which is the ratio of the turbulent rate constant to the laminar rate constant, is defined and its behavior as a function of the mean temperature fluctuations is described

Chinitz, W.↗
NASA NTRS1982

Investigation of the hydrochlorination of SiCl4

The hyrochlorination of SiC14 and m.g. silicon metal to produce SiHC13, was investigated. Reaction kinetic measurements were carried out to collect additional rate data at 525 C and 550 C. A theoretical study was carried out to provide a kinetic model and a rate equation for the hydrochlorination reaction. Results of this preliminary study show that the rate of formation of SiHC13 follows a pseudo first order kinetics. The rate constants were measured at three temperatures, 550 C, 500 C and 450 C, respectively. The activation energy was determined from the Arrhenius plot to give a value of 13.2 Kcal/mole. The design of a quartz reactor to measure reaction rates and equilibrium conversion of SiHC13 at reaction temperature up to 650 C was completed.

Mui, J. Y. P.↗
NASA NTRS1982

Surface profile changes of scuffed bearing surfaces

A phase locked interference microscope capable of resolving depth differences to 30 A and planar displacements of 6000 A was constructed for the examination of the profiles of bearing surfaces without physical contact. This instrument was used to determine surface chemical reactivity by applying a drop of dilute alcoholic hydrochloric acid and measuring the profile of the solid surface before and after application of this probe. Scuffed bearing surfaces reacted much faster than unscuffed ones, but bearing surfaces which had been previously exposed to lubricants containing an organic chloride reacted much more slowly. In a separate series of experiments, a number of stainless steel plates were heated in a nitrogen atmosphere to different temperatures and their reactivity examined later at room temperature. The change of surface contour as a result of the probe reaction followed an Arrhenius type relation with respect to heat treatment temperature. This result could have implications on the scuffing mechanism.

Lauer, J. L.↗
NASA NTRS1982

Experimental study of the thermal stability of hydrocarbon fuels

The thermal stability of two hydrocarbon fuels (premium diesel and regular diesel) was determined in a flow reactor under conditions representing operation of an aircraft gas turbine engine. Temperature was varied from 300 to 750 F (422 to 672 K) for fuel flows of 2.84 to 56.8 liters/hr (corresponding to 6.84 x 0.00010 to 1.63 x 0.010 kg/sec for regular diesel fuel and 6.55 x 0.00010 to 1.37 x 0.010 kg/sec for premium diesel fuel); test times varied between 1 and 8 hr. The rate of deposition was obtained through measurement of weight gained by metal discs fixed along the channel wall. The rate of deposit formation is best correlated by an Arrhenius expression. The sample discs in the flow reactor were varied among stainless steel, aluminum and brass; fuels were doped with quinoline, indole, and benzoyl perioxide to yield nitrogen or oxygen concentrations of approximately 1000 ppm. The most substantial change in rate was an increase in deposits for brass discs; other disc materials or the additives caused only small perturbations. Tests were also conducted in a static reactor at temperatures of 300 to 800 F for times of 30 min to 2 1/2 hr. Much smaller deposition was found, indicating the importance of fluid transport in the mechanism.

Marteney, P. J.↗
NASA NTRS1983

NASA interdisciplinary collaboration in tribology. A review of oxidational wear

An in-depth review of oxidational wear of metals is presented. Special emphasis is given to a description of the concept of oxidational wear and the formulation of an Oxidational Wear Theory. The parallelism between the formation of an oxide film for dry contact conditions and the formation of other surface films for a lubricated contact is discussed. The description of oxidational wear is prefaced with a unification of wear modes into two major classes of mild and severe wear including both lubricated and dry contacts. Oxidational wear of metals is a class of mild wear where protective oxide films are formed at real areas of contact and during the time of contact at temperataure T sub c. When the oxide reaches a critical thickness, frequently in the range of 1 to 3 microns, the oxide breaks up and eventually appears as a wear particle. These oxides are preferentially formed on plateaux which alternately carry the load as they reach their critical thickness and are removed. If the system is operated at elevated temperatures, thick oxides can form both out of contact and between the plateaux. Temperature is important in determining the structure of the oxide film present. Spinel oxide (Fe3O4) which forms above 300 C is more protective than the lower temperature rhomobohedral (alpha-Fe2O3) oxide which is abrasive. An Oxidational Wear Theory is derived using a modified Archard wear law expressed in terms of activation energy (Qp) and Arrhenius constant (Ap).

Quinn, T. F. J.↗
NASA NTRS1983

Rate processes in gas phase

Reaction-rate theory and experiment are given a critical review from the engineers' point of view. Rates of heavy-particle, collision-induced reaction in gas phase are formulated in terms of the cross sections and activation energies for reaction. The effect of cross section function shape and of excited state contributions to reaction both cause the slope of Arrhenius plots to differ from the true activation energy, except at low temperature. The master equations for chemically reacting gases are introduced, and dissociation and ionization reactions are shown to proceed primarily from excited states about kT from the dissociation or ionization limit. Collision-induced vibration, vibration-rotation, and pure rotation transitions are treated, including three-dimensional effects and conservation of energy, which have usually been ignored. The quantum theory of transitions at potential surface crossing is derived, and results are found to be in fair agreement with experiment in spite of some questionable approximations involved.

Hansen, C. F.↗