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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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
NASA NTRS1981

Kinetics of the reaction OH + HO2 yields H2O + O2 at 296 K

The rate constant of the title reaction was measured in a discharge-flow reactor by addition of excess HO2 from a movable double injector to a gas stream containing small concentrations of OH. The concentration of OH was measured by laser-induced fluorescence, HO2 by conversion to OH, and H and O by vacuum-UV resonance fluorescence. Five sets of experiments, each with different excess concentration of HO2, gave an average rate constant of (7.5 + or - 1.2) x 10 to the -11th cu cm/s where the error limits (single sigma) include uncertainties of all experimental parameters. This result is compared with other findings and is discussed in terms of its importance in stratospheric chemistry and in rate theory.

Sridharan, U. C.↗
NASA NTRS1986

Effects of test facility contaminants on supersonic hydrogen-air diffusion flames

Results are presented from an analytical assessment of the effects of NO and H2O in air on the ignition and reaction of hydrogen. Three flow models of the burning process were used, each including a 32 reaction chemistry mechanism. These models were a plug flow reactor to determine ignition and reaction times; a well-stirred reactor to assess flame stability or blow-off; and a parabolic Navier-Stokes code to examine the diffusion flame combustion. The diffusion flame was computed for a cold supersonic H2 jet coaxial with a supersonic air stream at a static temperature of 1100 K and a pressure of 1 atmosphere.

Rogers, R. Clayton↗
NASA NTRS1986

Effects of test facility contaminants on supersonic hydrogen-air diffusion flames

Results are presented from an analytical assessment of the effects of NO and H2O in air on the ignition and reaction of hydrogen. Three flow models of the burning process were used, each including a 32 reaction chemistry mechanism. These models were a plug flow reactor to determine ignition and reaction times; a well-stirred reactor to assess flame stability or blow-off, and a parabolic Navier Stokes code to examine the diffusion flame combustion. The diffusion flame was computed for a cold supersonic H2 jet coaxial with a supersonic air stream at a static temperature of 1100 K and a pressure of 1 atmosphere.

Rogers, R. Clayton↗
NASA NTRS1986

A kinetics study of the homogeneous and heterogeneous components of the HCl + ClONO2 reaction

The kinetics of the reaction HCl + ClONO2 to Cl2 + HNO3 were investigated at 298 K using a flow reactor with FTIR analysis to assess the importance of this reaction for stratospheric chemistry. The observed reaction was characteristic of a heterogeneous process; an upper limit of 5 x 10 to the -18th cu cm/molecule per s was obtained for the homogeneous gas phase rate constant. From calculations of the first order wall rate constant, estimates were made of the reaction rate on stratospheric aerosols. Because both HCl and ClONO2 need to be adsorbed on the particle surface, the reaction will be of negligible importance under most stratospheric conditions.

Friedl, Randall R.↗
NASA NTRS1988

Laboratory studies of sticking coefficients and heterogeneous reactions important in the Antarctic stratosphere

Laboratory studies of sticking coefficients of H2O, HCl, Cl2, and HNO3 on ice and heterogeneous reactions of ClONO2 with ice or HCl/ice have been performed in a fast flow reactor. A quadrupole mass spectrometer with electron impact ionization was used as a detector. Measured sticking coefficients are: 0.3 (+0.7, -0.1) for H2O, 0.4 (+0.6, -0.2) for HCL, less than 0.0001 for Cl2, and 0.3 (+0.7, -0.1) for HNO3 at 200 K. The reaction probability of ClONO2 on ice was found to be 0.06 (+ or - 0.03) while HOCl was observed as a sole product in the gas phase. With HCl present in ice, the reaction probability of ClONO2 is greatly enhanced, approaching 0.27 (+0.73, -0.13) while molecular chlorine was found to be the major product in the gas phase. Another reaction product was nitric acid which remained in the solid phase. Since the polar stratospheric clouds contain ice particles or possibly HCl/ice particles on the surface, the present results should be a major factor in producing the observed springtime ozone depletion in the Antarctic stratosphere.

Leu, Ming-Taun↗
NASA NTRS1988

Antarctic ozone depletion chemistry - Reactions of N2O5 with H2O and HCl on ice surfaces

In a study concerning Antarctic ozone depletion, reactions of dinitrogen pentoxide with water and hydrochloric acid were studied on ice surfaces in a Knudsen cell flow reactor. The N2O5 reacted on ice at 185 K to form condensed-phase nitric acid (HNO3). This reaction may provide a sink for odd nitrogen, NO(x), during the polar winter, a requirement in nearly all models of Antarctic ozone depletion. The reaction of N2O5 on HCl-ice surfaces at 185 K produced gaseous nitryl chloride (ClNO2) and condensed-phase HNO3 and proceeded until all of the HCl within the ice was depleted. The ClNO2 which did not react or condense on ice at 185 K, can be readily photolyzed in the Antarctic spring to form atomic chlorine for catalytic ozone destruction cycles. The other photolysis product, gaseous nitrogen dioxide may be important in the partitioning of NO(x) between gaseous and condensed phases in the Antarctic winter.

Tolbert, Margaret A.↗
NASA NTRS1988

Heterogeneous interactions of chlorine nitrate, hydrogen chloride, and nitric acid with sulfuric acid surfaces at stratospheric temperatures

The heterogeneous interactions of ClONO2, HCl, and HNO3 with sulfuric acid surfaces were studied using a Knudsen cell flow reactor. The surfaces studied, chosen to simulate global stratospheric particulate, were composed of 65-75 percent H2SO4 solutions at temperatures in the range -63 to -43 C. Heterogeneous loss, but not reaction, of HNO3 and HCl occurred on these surfaces; the measured sticking coefficients are reported. Chlorine nitrate reacted on the cold sulfuric acid surfaces, producing gas-phase HOCl and condensed HNO3. CLONO2 also reacted with HCl dissolved in the 65-percent H2SO4 solution at -63 C, forming gaseous Cl2. In all cases studied, the sticking and/or reaction coefficients were much larger for the 65-percent H2SO4 solution at -63 C than for the 75-percent solution at -43 C.

Tolbert, Margaret A.↗
NASA NTRS1988

Heterogeneous reactions of N2O5 with H2O and HCl on ice surfaces - Implications for Antarctic ozone depletion

This paper reports on the measurements of reaction probabilities for heterogeneous reaction of N2O5 with H2O and HCl on ice surfaces at 195 K, using a fast-flow reactor coupled with a quadrupole mass spectrometer. The reaction probability for N2O5 on pure-water ice was found to be 0.028 + or - 0.011, with nitric acid in the solid phase as the sole product. In the presence of HCl in ice, the probability of N2O5 reaction was enhanced (to 0.037); the reaction produced, besides solid-phase nitric acid, ClNO2 and ClONO which were released into the gas phase within a few milliseconds. The latter two compounds can be readily photolyzed in the austral spring to form active chlorine which would remove stratospheric ozone. It is suggested that, since the polar stratospheric clouds are believed to contain HCl-ice mixture on the surface, the reactions of N2O5 on H2O/HCl particles is a major factor in the Antarctic springtime ozone depletion.

Leu, Ming-Taun↗
NASA NTRS1988

Collisional quenching of atoms and molecules on spacecraft thermal protection surfaces

Preliminary results of a research program to determine energy partitioning in spacecraft thermal protection materials due to atom recombination at the gas-surface interface are presented. The primary focus of the research is to understand the catalytic processes which determine heat loading on Shuttle, Aeroassisted OTV, and NASP thermal protection surfaces in nonequilibrium flight regimes. Highly sensitive laser diagnostics based on laser-induced fluorescence and resonantly-enhanced multiphoton ionization spectroscopy are used to detect atoms and metastable molecules. At low temperatures, a discharge flow reactor is employed to measure deactivation/recombination coefficients for O-atoms, N-atoms, and O2. Detection methods are presented for measuring O-atoms, O2 and N2, and results for deactivation of O2 and O-atoms on reaction-cured glass and Ni surfaces. Both atom recombination and metastable product formation are examined. Radio-frequency discharges are used to produce highly dissociated beams of atomic species at energies characteristic of the surface temperature. Auger electron spectroscopy is employed as a diagnostic of surface composition in order to accurately define and control measurement conditions.

Marinelli, W. J.↗
NASA NTRS1988

Heterogeneous chemistry related to Antarctic ozone depletion: Reaction of ClONO2 and N2O5 on ice surfaces

Laboratory studies of heterogeneous reactions of possible importance for Antarctic ozone depletion were performed. In particular, the reactions of chlorine nitrate (ClONO2) and dinitrogen pentoxide (N2O5) were investigated on ice and HCl/ice surfaces. These reactions occur on the surfaces of polar stratospheric clouds (PSCs) over Antarctica. One reaction transforms the stable chlorine reservoir species (ClONO2 and HCl) into photochemically active chlorine in the form of HOCl and Cl2. Condensation of HNO3 in the reactions removes odd nitrogen from the stratosphere, a requirement in nearly all models of Antarctic ozone depletion. Other reactions may also be important for Antarctic ozone depletion. Like the reactions of chlorine nitrate, these reactions deplete odd nitrogen through HNO3 condensation. In addition, one reaction converts a stable chlorine reservior species (HCl) into photochemically active chlorine (ClNO2). These reactions were studied with a modified version of a Knudsen cell flow reactor.

Tolbert, Margaret A.↗
NASA NTRS1990

Synthesis, characterization and evaluation of CO-oxidation catalysts for high repetition rate CO2 TEA lasers

An extremely active class of noble metal catalysts supported on titania was developed and fabricated at Hughes for the recombination of oxygen (O2) and carbon monoxide (CO) in closed-cycle CO2 TEA lasers. The incipient wetness technique was used to impregnate titania and alumina pellets with precious metals including platinum and palladium. In particular, the addition of cerium (used as an oxygen storage promoter) produced an extremely active Pt/Ce/TiO2 catalyst. By comparison, the complementary Pt/Ce/ gamma-Al2O3 catalyst was considerably less active. In general, chloride-free catalyst precursors proved critical in obtaining an active catalyst while also providing uniform metal distributions throughout the support structure. Detailed characterization of the Pt/Ce/TiO2 catalyst demonstrated uniform dendritic crystal growth of the metals throughout the support. Electron spectroscopy for Chemical Analysis (ESCA) analysis was used to characterize the oxidation states of Pt, Ce and Ti. The performance of the catalysts was evaluated with an integral flow reactor system incorporating real time analysis of O2 and CO. With this system, the transient and steady-state behavior of the catalysts were evaluated. The kinetic evaluation was complemented by tests in a compact, closed-cycle Hughes CO2 TEA laser operating at a pulse repetition rate of 100 Hz with a catalyst temperature of 75 to 95 C. The Pt/Ce/TiO2 catalyst was compatible with a C(13)O(16)2 gas fill.

Moser, Thomas P.↗
NASA NTRS1990

Rare-isotope and kinetic studies of Pt/SnO2 catalysts

Closed-cycle pulsed CO2 laser operation requires the use of an efficient CO-O2 recombination catalyst for these dissociation products which otherwise would degrade the laser operation. The catalyst must not only operate at low temperatures but also must operate efficiently for long periods. In the case of the Laser Atmospheric Wind Sounder (LAWS) laser, an operational lifetime of 3 years is required. Additionally, in order to minimize atmospheric absorption and enhance aerosol scatter of laser radiation, the LAWS system will operate at 9.1 micrometers with an oxygen-18 isotope CO2 lasing medium. Consequently, the catalyst must not only operate at low temperatures but must also preserve the isotopic integrity of the rare-isotope composition in the recombination mode. Several years ago an investigation of commercially available and newly synthesized recombination catalysts for use in closed-cycle pulsed common and rare-isotope CO2 lasers was implemented at the NASA Langley Research Center. Since that time, mechanistic efforts utilizing both common and rare oxygen isotopes have been implemented and continue. Rare-isotope studies utilizing commercially available platinum-tin oxide catalyst have demonstrated that the catalyst contributes oxygen-16 to the product carbon dioxide thus rendering it unusable for rare-isotope applications. A technique has been developed for modification of the surface of the common-isotope catalyst to render it usable. Results of kinetic and isotope label studies using plug flow, recycle plug flow, and closed internal recycle plug flow reactor configuration modes are discussed.

Upchurch, Billy T.↗
NASA NTRS1990

Performance of alumina-supported Pt catalysts in an electron-beam-sustained CO2 laser amplifier

The performance of an alumina-supported Pt catalyst system used to maintain the gas purity in an electron-beam-sustained (636) isotope CO2 laser amplifier has been tested. The system characteristics using the two-zone, parallel flow reactor were determined for both continuous- and end-of-day reactor operation using on-line mass spectrometric sampling. The laser amplifier was run with an energy loading of typically 110 J-l/atm and an electron-beam current of 4 mA/sq cm. With these conditions and a pulse repetition frequency of 10 Hz for up to 10,000 shots, increases on the order of 100 ppm O2 were observed with the purifier on and 150 ppm with it off. The 1/e time recovery time was found to be approximately 75 minutes.

Cunningham, D. L.↗
NASA NTRS1990

The microwave spectrum of the AlO radical

The rotational spectrum of the aluminum monoxide radical in the ground electronic state X 2Sigma(+) was observed in the millimeter- and submillimeter-wave region. Aluminum monoxide radicals were generated directly in a flow reactor absorption cell by the reaction of N2O with aluminum vaporized from a high-temperature crucible. The observed spectrum was analyzed to yield molecular constants including the rotational constant, centrifugal distortion constant, spin-rotation interaction constant, magnetic hyperfine interaction constants, and nuclear quadrupole coupling constant.

Yamada, Chikashi↗
NASA NTRS1990

Oxidation kinetics of model compounds of metabolic waste in supercritical water

In this NASA-funded study, the oxidation kinetics of methanol and ammonia in supercritical water have been experimentally determined in an isothermal plug flow reactor. Theoretical studies have also been carried out to characterize key reaction pathways. Methanol oxidation rates were found to be proportional to the first power of methanol concentration and independent of oxygen concentration and were highly activated with an activation energy of approximately 98 kcal/mole over the temperature range 480 to 540 C at 246 bar. The oxidation of ammonia was found to be catalytic with an activation energy of 38 kcal/mole over temperatures ranging from 640 to 700 C. An elementary reaction model for methanol oxidation was applied after correction for the effect of high pressure on the rate constants. The conversion of methanol predicted by the model was in good agreement with experimental data.

Webley, Paul A.↗
NASA NTRS1991

Jet-A reaction mechanism study for combustion application

Simplified chemical kinetic reaction mechanisms for the combustion of Jet A fuel was studied. Initially, 40 reacting species and 118 elementary chemical reactions were chosen based on a literature review. Through a sensitivity analysis with the use of LSENS General Kinetics and Sensitivity Analysis Code, 16 species and 21 elementary chemical reactions were determined from this study. This mechanism is first justified by comparison of calculated ignition delay time with the available shock tube data, then it is validated by comparison of calculated emissions from the plug flow reactor code with in-house flame tube data.

Lee, Chi-Ming↗
NASA NTRS1991

Jet-A reaction mechanism study for combustion application

Simplified chemical kinetic reaction mechanisms for the combustion of Jet A fuel are studied. Initially 40 reacting species and 118 elementary chemical reactions were chosen based on the literature review of previous works. Through a sensitivity analysis with the use of LSENS General Kinetics and Sensitivity Analysis Code, 16 species and 21 elementary chemical reactions were determined from this study. This mechanism is first justified by comparison of calculated ignition delay time with available shock tube data, then it is validated by comparison of calculated emissions from plug flow reactor code with in-house flame tube data.

Lee, Chi-Ming↗
NASA NTRS1992

A molecular beam mass spectrometric study of the formation and photolysis of C(lc)lO dimer

A study of the chlorine oxides present at temperatures and pressures typical of the Antarctic stratosphere was carried out. A series of low temperature flow reactors was constructed and used in conjunction with molecular beam mass spectrometric techniques to identify species and characterize their kinetic behavior at temperatures of -20 to -70 C and pressures of from 30 to 130 Torr. It was found that the gas phase chlorine-oxygen system was quite complex at low temperatures. ClO dimer was identified and found to be thermodynamically very stable under stratospheric conditions. It was also found that any system which contained ClO also contained a larger oxide. The oxide was identified as Cl2O3. A survey of possible higher oxides, which have been postulated as possible chlorine sinks in the stratosphere, was also carried out. The rate of formation of ClO dimer was measured as a function of temperature and pressure. Measurements were made of both the decay of ClO and the formation of the dimer. By comparing these rates it was determined that virtually all of the ClO was converted to the dimer under stratospheric conditions, and that the other ClO reactions were not important under these conditions.

Greene, Frank T.↗