Search NASA⌕ Search

SEARCH · Search NASA

Results for “GAS DISSOCIATION”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
NASA NTRS1997

Kinetics and Thermochemistry of the Br((sup 2)P3/2) + NO2 Association Reaction

A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of the Br((sup 2)P3/2) + NO2 association reaction as a function of temperature (259-432 K) pressure (12.5 - 700 Torr), and buffer gas identity (He, Ar, H2, N2, CO2, CF4, SF6). The reaction is found to be in the falloff regime between third and second order over the entire range of conditions investigated. At temperatures below 350 K, the association reaction is found to be irreversible on the time scale of the experiment (approximately 30 ms). At higher temperatures reversible addition is observed, allowing equilibrium constants for BrNO2 formation and dissociation to be determined. Second- and third-law analyses of the equilibrium data are in only fair agreement and lead to the following thermochemical parameters for the association reaction: Delta-H(298) = 19.6 +/- 1.7 kcal/mol, Delta-H(0) = -18.6 +/- 2.0 kcal/mol, Delta-S(298) = 29.3 +/- 4.2 cal/mol/K, Delta-H(sub f)(sub 298)(BrNO2) = 17.0 +/-1.8 kcal/mol(uncertainties are 2 sigma estimates of absolute accuracy). The value for Delta-H(0) determined in this study has been employed to calculate k(sub 0)(sup SC), the low-pressure third-order rate coefficient in the strong collision limit, by using the method of Troe; calculated values of k(sub 0)(sup SC) are inconsistent with experimental results unless Delta-H(0) is assigned a value near the lower limit derived from analysis of the high-temperature approach to equilibrium data, i.e. delta-H(0) approximately equals -16.6 kcal/mol. A potential source of systematic error in the calculation of both k(sub 0)(sup SC) and the absolute entropy of BrNO2 results from the complete lack of knowledge of the energies and degeneracies of the electronic states of BrNO3. The procedure developed by Troe and co-workers has been employed to extrapolate experimental falloff curves to the low- and high-pressure limits. Derived values for k(sub 0)(M,298K) in units of 10(exp -31) cm(exp 6)/sq molecule/s range from 2.75 for M = He to 6.54 for M = CO2; 2 sigma uncertainties are estimated to be +/- 20%. Values for k(sub 0)(N2,T) in units of 10(exp -31) cm(exp 6)/sq molecule/s are 5.73 at 259 K, 4.61 at 298 K, and 3.21 at 346 K; the observed temperature dependence for k(sub 0)(N2,T) is consistent with the theoretical temperature dependence for Beta(sub c)k(sub 0)(sup SC). Values for k(sub infinity)(T) in units of 10(exp -11) cu cm/molecule/s are 2.86 at 259 K, 3.22 at 298 K, and 3.73 at 346 K; 2 sigma uncertainties are estimated to be a factor of 2. Approximate falloff parameters in a convenient format for atmospheric modeling are also derived.

Kreutter, K. D.↗
NASA NTRS2004

Photoionization in Ultraviolet Processing of Astrophysical Ice Analogs at Cryogenic Temperatures

Two recent experimental studies have demonstrated that amino acids or amino acid precursors are generated when astrophysical ice analogs are subjected to ultraviolet (UV) irradiation at cryogenic temperatures. Understanding the complete phenomenology of photoprocessing is critical to elucidating chemical reaction mechanisms that can function within an ice matrix under very cold conditions. Pushing beyond the much better characterized study of photolytic dissociation of chemical bonds through electronic excitation, this work explored the ability of UV radiation present in the interstellar medium to ionize small molecules embedded in ices. Quantum chemical calculations, including bulk solvation effects, were used to study the ionization of hydrogen (H2), water, and methanol (CH3OH) bound in small clusters of water. Ionization potentials were found to be much smaller in the condensed phase than in the gas phase; even a small cluster can account for large changes in the ionization potentials in ice, as well as the known formation of an OH--H3O+ pair in the case of H2O photoionization. To gauge the impact of photoionization on subsequent grain chemistry, the reaction between OH and CO in the presence of H3O+ was studied and compared with the potential energy surface without hydronium present, which is relevant to chemistry following photolysis. The differences indicate that the reaction is somewhat more likely to proceed to products (H + CO2) in the case of photoionization.

Woon, David E.↗
NASA NTRS1961

Recombination of Hydrogen-Air Combustion Products in an Exhaust Nozzle

Thrust losses due to the inability of dissociated combustion gases to recombine in exhaust nozzles are of primary interest for evaluating the performance of hypersonic ramjets. Some results for the expansion of hydrogen-air combustion products are described. Combustion air was preheated up to 33000 R to simulate high-Mach-number flight conditions. Static-temperature measurements using the line reversal method and wall static pressures were used to indicate the state of the gas during expansion. Results indicated substantial departure from the shifting equilibrium curve beginning slightly downstream of the nozzle throat at stagnation pressures of 1.7 and 3.6 atmospheres. The results are compared with an approximate method for determining a freezing point using an overall rate equation for the oxidation of hydrogen.

Lezberg, Erwin A.↗
NASA NTRS1960

Interactions between Ground State Oxygen Atoms and Molecules: O - O and O (sub2) - O (sub2)

Potential energy curves for O - O interactions corresponding to the X (sup 3) Sigma - g, 1 delta g, 1 Sigma plus g, 3 delta u, A3 Sigma plus u, 1 Sigma - u, and B3 Sigma states of O (sub 2) have been calculated from spectroscopic data by the Rydberg‐Klein‐Rees method. Curves for the remaining twelve states of O (sub 2) dissociating to ground state atoms have been obtained from relations derived from approximate quantum‐mechanical calculations, and checked against the meager experimental information available. Two semi‐independent calculations have been made, and are in good agreement with each other. The quantum‐mechanical relations also lead to an approximate O (sub 2) - O (sub 2) interaction, which is consistent with interactions derived from vibrational relaxation times and from high‐temperature gas viscosity data.

Vanderslice, Joseph T.↗
NASA NTRS1990

Laboratory studies of photodissociation processes relevant to the formation of cometary radicals

The strength of the C2(d 3 Pi g yields a 3 Pi u) Swan band emission in the spectra of cometary comae identifies this species as a prominent constituent of the coma gas. It was previously suggested that the formation of cometary C2 proceeds via the secondary photolysis of the C2H radical. The detection of C2H in the interstellar medium and the recent analysis of the radial variation in C2(delta V=O) surface brightness of Comet Halley support the postulate that C2 is a third-generation molecule. Measurement of the C2 and C2H translational energy distributions produced from the multiphoton dissociation (MPD) of acetylene at 193 nm are identified . Time-resolved FTIR emission studies of the nascent C2H radical formed in the C2H2 yields C2H + H reaction verify that this species is produced both vibrationally and electronically excited. A survey of the internal energy distributions of the C2 fragments produced from the MPD of acetylene using a high intensity ArF laser is currently in progress in the laboratory. Recent experiments have focused on the measurement of rotational energy distribution for the C2(A 1 Pi u, a 3 Pi u) fragments. The C2(a 3 Pi u) detection capability is currently being improved by performing this experiment in a molecular beam, thus allowing for discrimination between initial emission and laser-induced fluorescence (LIF). Although the experiments performed to date provide considerable evidence in support of C2H yields C2 + H reaction, there is an important distinction to be made when comparing the laboratory conditions to those typically found in comets. The C2H radicals generated in the laboratory experiments are formed vibrationally and/or electronically excited. Any rotationally/vibrationally excited C2H present in cometary comae will quickly undergo radiative relaxation in the infrared to their lowest rotational and vibrational state. Experiments are currently under way to confirm the cometary formation of C2 via the VUV dissociation of cold C2H.

Urdahl, R. S.↗
NASA NTRS2014

High-Precision Measurement of Eu/Eu* in Geological Glasses via LA-ICP-MS Analysis

Elemental fractionation during laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis has been historically documented between refractory and volatile elements. In this work, however, we observed fractionation between light rare earth elements (LREEs) and heavy rare earth elements (HREEs) when using ablation strategies involving large spot sizes (greater than 100 millimeters) and line scanning mode. In addition: (1) ion yields decrease when using spot sizes above 100 millimeters; (2) (Eu/Eu*)(sub raw) (i.e. Europium anomaly) positively correlates with carrier gas (He) flow rate, which provides control over the particle size distribution of the aerosol reaching the ICP; (3) (Eu/Eu*)(sub raw) shows a positive correlation with spot size, and (4) the changes in REE signal intensity, induced by the He flow rate change, roughly correlate with REE condensation temperatures. The REE fractionation is likely driven by the slight but significant difference in their condensation temperatures. Large particles may not be completely dissociated in the ICP and result in preferential evaporation of the less refractory LREEs and thus non-stoichiometric particle-ion conversion. This mechanism may also be responsible for Sm-Eu-Gd fractionation as Eu is less refractory than Sm and Gd. The extent of fractionation depends upon the particle size distribution of the aerosol, which in turn is influenced by the laser parameters and matrix. Ablation pits and lines defined by low aspect ratios produce a higher proportion of large particles than high aspect ratio ablation, as confirmed by measurements of particle size distribution in the laser induced aerosol. Therefore, low aspect ratio ablation introduces particles that cannot be decomposed and/or atomized by the ICP and thus results in exacerbated elemental fractionation. Accurate quantification of REE concentrations and Eu/Eu* requires reduction of large particle production during laser ablation. For the reference materials analyzed in this work, the 100 millimeters spot measurements of Eu/Eu* agreed with GeoRem preferred values within 3 percent. Our long-term analyses of Eu/Eu* in MPI-DING glass KL-2G and USGS glass BIR-1G were reproducible at 3 percent (2 RSD).

geological glasses↗
NASA NTRS1994

Viscous Shock-Layer Analysis of Two-Dimensional and Axisymmetric Flows

Results are obtained for cylindrical leading edges of proposed transatmospheric vehicles by employing a two-dimensional viscous shock-layer code for nonequilibrium gas flows. The accuracy and efficiency of the planar code is verified through detailed comparisons with other predictions. This study includes results for 6-deg half-angle bodies with nose radii ranging from 0.01 to 2.0 ft for both cylindrically blunted wedges and spherically blunted cones (included for comparison). Some results are presented as a ratio of the noncatalytic to the corresponding fully catalytic heating value to illustrate the maximum potential for a heating reduction in dissociated nonequilibrium flows. Generally, this ratio and the individual heating rates are smaller for cylindrically blunted wedges with small nose radii as compared to the spherically blunted cones (for the same nose radius). Therefore, a larger potential exists for heating reduction in cylindrically blunted as compared with the spherically blunted surfaces. However, the results presented at higher altitudes (where the slip effects become important) show that the spherically, blunted nose gives lower stagnation-point heating due to stronger merged shock-layer effects as compared with a cylindrically blunted nose.

Gupta, Roop N.↗
NASA NTRS1992

Estimation of excitation energy of diatomic molecules in expanding nonequilibrium flows

The energy contained in the highly excited vibrational and rotational states in a diatomic gas in a thermochemical nonequilibrium state during expansion is estimated. The estimation is made on the assumption that the populations of the vibrational and rotational states, when normalized by their respective equilibrium values, are describable by simple functions containing no more than four arbitrary parameters. A cubic polynomial, a logarithmic-cubic polynomial, and a bimodal step function are used for this purpose. The four parameters are determined by imposing conditions known at the ground state and the dissociation limit and the mass conservation law. The energy in excess of that accounted for by assuming a Boltzmann distribution of these states, defined here as excess excitation energy, is calculated for N2, O2, NO, CO, OH, and H2. A calculation made for a typical nozzle flow shows that the excess energy may reach 6 percent of the total enthalpy of the flow, and that the flow velocity may decrease by as much as 4 percent due to the nonequilibrium excitation phenomenon.

Park, Chul↗
NASA NTRS1979

Study of a rare-gas transverse fast discharge

An experimental and analytical study of a Blumlein-type transverse fast discharge operating with He and Xe are presented. An electro-optical voltage probe was used to measure the discharge voltage, and the measured voltages were in agreement with the computed voltages. The analytical model was used to predict the dependence of the discharge efficiency for producing metastables and ions on the important plasma and external circuit parameters. In He the ion efficiency is greater than the metastable efficiency, while in Xe it is the opposite; the He ion efficiencies are much larger than in Xe, while Xe metastable efficiencies are much larger than in He. These differences between Xe and He are accounted by the large dissociative recombination rate of Xe compared with He.

Chubb, D. L.↗
NASA NTRS1989

Classical trajectory studies of gas phase reaction dynamics and kinetics using ab initio potential energy surfaces

Strategies for constructing global potential energy surfaces from a limited number of accurate ab initio electronic energy calculations are discussed. Generally, these data are concentrated in small regions of configuration space (e.g., in the vicinity of saddle points and energy minima) and difficulties arise in generating a potential function that is globally well-behaved. Efficient computer codes for carrying out classical trajectory calculations on vector and parallel processors are also described. Illustrations are given from recent work on the following chemical systems: Ca + HF yields CaF + H, H + H + H2 yields H2 + H2, N + O2 yields NO + O and O + N2 yields NO + N. The dynamics and kinetics of metathesis, dissociation, recombination, energy transfer and complex formation processes will be discussed.

Jaffe, Richard L.↗
NASA NTRS1989

Computational aerothermodynamics

Computational aerothermodynamics concerns the coupling of real gas effects with equations of motion to include thermochemical rate processes for chemical and energy exchange phenomena. These processes concern the creation and destruction of gas species by chemical reactions and the transfer of energy between the various species and between the various energy modes (e.g., translation, rotation, vibration, ionization, dissociation/recombination, etc.) of the species. To gain some insight into when such phenomena occur for current and future aerospace flight vehicles the author shows the flight regimes of some typical vehicles (e.g., Concord, aerospace plane, Space Shuttle, associated space transfer vehicles, Apollo entry vehicle, etc.) in terms of flight altitude and flight speed. Also indicated are regimes where chemical reactions such as dissociation and ionization are important and where nonequilibrium thermochemical phenomena are important.

Deiwert, George S.↗
NASA NTRS1982

Shock waves in Orion

Results are presented of shock modeling of the H2, CO, and OH infrared emission lines in the Becklin-Neugebauer-Kleinmann-Low region of the Orion Molecular Cloud-1. The strength of the preshock magnetic field is estimated to be approximately 1 mGs, which indicates that magnetic pressure may help support the gas in this region. Determinations of the shock speed and the preshock density, along with the measured extent of the gas, show that the momentum and energy in the swept-up shocked material is rather high compared with the usual estimates of the available momentum and energy from the embedded sources. The abundance of shock-heated CO is found to be close to the solar abundance of carbon, and the extinction to the 2-micron region of H2 is approximately 2-2.5 mag. In addition, it is determined that the high-velocity wings of the H2 emission lines are most likely produced either behind fast dissociative shock waves or behind slower nondissociative shock waves traversing high-speed material.

Hollenbach, D.↗
NASA NTRS1993

Aerothermodynamic heating due to shock wave/laminar boundary-layer interactions in high-enthalpy hypersonic flow

The interaction between a swept shock wave and a laminar boundary layer was investigated experimentally in high-enthalpy hypersonic flow. The effect of high-temperature, real gas physics on the interaction was examined by conducting tests in air and helium. Heat transfer measurements were made on the surface of a flat plate and a shock-generating fin using thin-film resistance sensors for fin incidence angles of 0, 5, and 10 deg at Mach numbers of 6.9 in air and 7.2 in helium. The experiments were conducted in the NASA HYPULSE expansion tube, an impulse-type facility capable of generating high-enthalpy, high-velocity flow with freestream levels of dissociated species that are particularly low. The measurements indicate that the swept shock wave creates high local heat transfer levels in the interaction region, with the highest heating found in the strongest interaction. The maximum measured heating rates in the interaction are order of magnitude greater than laminar flat plate boundary layer heating levels at the same location.

Hackett, Charles M.↗
NASA NTRS1963

Performance Capability of Single-Cavity Vortex Gaseous Nuclear Rockets

An analysis was made to determine the maximum powerplant thrust-to-weight ratio possible with a single-cavity vortex gaseous reactor in which all the hydrogen propellant must diffuse through a fuel-rich region. An assumed radial temperature profile was used to represent conduction, convection, and radiation heat-transfer effects. The effect of hydrogen property changes due to dissociation and ionization was taken into account in a hydrodynamic computer program. It is shown that, even for extremely optimistic assumptions of reactor criticality and operating conditions, such a system is limited to reactor thrust-to-weight ratios of about 1.2 x 10(exp -3) for laminar flow. For turbulent flow, the maximum thrust-to-weight ratio is less than 10(exp -3). These low thrusts result from the fact that the hydrogen flow rate is limited by the diffusion process. The performance of a gas-core system with a specific impulse of 3000 seconds and a powerplant thrust-to-weight ratio of 10(exp -2) is shown to be equivalent to that of a 1000-second advanced solid-core system. It is therefore concluded that a single-cavity vortex gaseous reactor in which all the hydrogen must diffuse through the nuclear fuel is a low-thrust device and offers no improvement over a solid-core nuclear-rocket engine. To achieve higher thrust, additional hydrogen flow must be introduced in such a manner that it will by-pass the nuclear fuel. Obviously, such flow must be heated by thermal radiation. An illustrative model of a single-cavity vortex system employing supplementary flow of hydrogen through the core region is briefly examined. Such a system appears capable of thrust-to-weight ratios of approximately 1 to 10. For a high-impulse engine, this capability would be a considerable improvement over solid-core performance. Limits imposed by thermal radiation heat transfer to cavity walls are acknowledged but not evaluated. Alternate vortex concepts that employ many parallel vortices to achieve higher hydrogen flow rates offer the possibility of sufficiently high thrust-to-weight ratios, if they are not limited by short thermal-radiation path lengths.

Ragsdale, Robert G.↗
NASA NTRS2011

Photolysis of Pure Solid O3 and O2 Films at 193nm

We studied quantitatively the photochemistry of solid O3 and O2 films at 193 nm and 22 K with infrared spectroscopy and microgravimetry. Photolysis of pure ozone destroyed O3, but a small amount of ozone remained in the film at high fluence. Photolysis of pure O2 produced O3 in an amount that increased with photon fluence to a stationary level. For both O2 and O3 films, the O3:O2 ratio at large fluences is ?0.07, about two orders of magnitude larger than those obtained in gas phase photolysis. This enhancement is attributed to the increased photodissociation of O2 due to photoabsorption by O2 dimers, a process significant at solid-state densities. We obtain initial quantum yield for ozone synthesis from solid oxygen, phi (O3) = 0.24 0.06, and quantum yields for destruction of O3 and O2 in their parent solids, phi(-O3) = 1.0 0.2 and phi(-O2) = 0.36 0.1. Combined with known photoabsorption cross sections, we estimate probabilities for geminate recombination of 0.5 0.1 for O3 fragments and 0.88 0.03 for oxygen atoms from O2 dissociation. Using a single parameter kinetic model, we deduce the ratio of reaction cross sections for an O atom with O2 vs. O3 to be 0.1 0.2. The general good agreement of the model with the data suggests the validity of the central assumption of efficient energy and spin relaxation of photofragments in the solid prior to their reactions with other species.

Raut, U.↗
NASA NTRS2012

Modeling of Laser Vaporization and Plume Chemistry in a Boron Nitride Nanotube Production Rig

Flow in a pressurized, vapor condensation (PVC) boron nitride nanotube (BNNT) production rig is modeled. A laser provides a thermal energy source to the tip of a boron ber bundle in a high pressure nitrogen chamber causing a plume of boron-rich gas to rise. The buoyancy driven flow is modeled as a mixture of thermally perfect gases (B, B2, N, N2, BN) in either thermochemical equilibrium or chemical nonequilibrium assuming steady-state melt and vaporization from a 1 mm radius spot at the axis of an axisymmetric chamber. The simulation is intended to define the macroscopic thermochemical environment from which boron-rich species, including nanotubes, condense out of the plume. Simulations indicate a high temperature environment (T > 4400K) for elevated pressures within 1 mm of the surface sufficient to dissociate molecular nitrogen and form BN at the base of the plume. Modifications to Program LAURA, a finite-volume based solver for hypersonic flows including coupled radiation and ablation, are described to enable this simulation. Simulations indicate that high pressure synthesis conditions enable formation of BN vapor in the plume that may serve to enhance formation of exceptionally long nanotubes in the PVC process.

Gnoffo, Peter A.↗
NASA NTRS1995

Hydrocarbon Ions in the Ionospheres of Titan and Jupiter

Two examples are given of models of ion chemistry in reducing atmospheres: Titan, which is a satellite of Saturn, and Jupiter, the largest of the gas giants. In both ionospheres, layers of hydrocarbon and/or C, H, and N-containing ions have been predicted to appear, with larger ions dominating at lower altitudes. Altitude profiles are presented for individual C1- and C2-hydrocarbon ions and larger ions that are represented for example, as C(x)H(y)(+) and C(x)H(y)N(x)(+). The accuracy of the predictions is, however, limited by the availability of information about the chemistry of these ions. In addition to rate coefficients and product channels for ion-molecule reactions, dissociative recombination coefficients and branching ratios are needed for many hydrocarbon and and related ions.

Fox, J. L.↗
NASA NTRS2002

Theoretical Study of Decomposition Pathways for HArF and HKrF

To provide theoretical insights into the stability and dynamics of the new rare gas compounds HArF and HKrF, reaction paths for decomposition processes HRgF to Rg + HF and HRgF to H + Rg + F (Rg = Ar, Kr) are calculated using ab initio electronic structure methods. The bending channels, HRgF to Rg + HF, are described by single-configurational MP2 and CCSD(T) electronic structure methods, while the linear decomposition paths, HRgF to H + Rg + F, require the use of multi-configurational wave functions that include dynamic correlation and are size extensive. HArF and HKrF molecules are found to be energetically stable with respect to atomic dissociation products (H + Rg + F) and separated by substantial energy barriers from Rg + HF products, which ensure their kinetic stability. The results are compatible with experimental data on these systems.

Chaban, Galina M.↗