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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
NASA NTRS1983

Relative rate constants for the reactions of atomic oxygen with HO2 anad OH radicals

Relative rate constants for the reactions O + HO2 - OH + O2 (1) and O + OH - H + O2 (2) were obtained by using the discharge-flow resonance fluorescence technique at 2 torr total pressure and 299 K. HO2 radicals were generated by reacting atomic hydrogen with an excess of O2. Quasi-steady-state concentrations of OH and HO2 were established in the presence of excess atomic oxygen. Observed concentration ratios, namely the ratio of the OH concentration to the HO2 concentration, resulted in a value of 1.7 + or 0.2 for k1/k2. The error limits are twice the standard deviation obtained from the data analysis. Overall experimental error is estimated to be + or - 25 percent. This result confirms earlier direct measurements of k1 and k2 which required knowledge of absolute radical or atomic oxygen concentrations.

Keyser, L. F.↗
NASA NTRS1986

OH radical measurements by optical absorption spectroscopy

The long path absorption spectroscopy (LPA) measurement of OH utilizes the strong UV absorption spectrum of the molecule with well resolved rotational lines around 308 nm. The light source consists of an Ar ion laser pumped CW dye laser, the output of which is frequency doubled to emit a spectrally smooth light profile of 0.1 nm FWHM at 308 nm. This is considerably broader than the sharp (0.0018 nm wide) absorption features of OH and also wider than the total spectral region (0.06 nm) scanned around the OH lines. For field measurements a Cassegrain-type telescope expands the small diameter of the original laser beam by a factor of 50 to about a 0.25-m diameter in order to reduce the divergence of the beam as well as its mean photon flux density, thus reducing the maximum self-generated OH concentration to 40,000 cu. cm. The light is passed into the open atmosphere and reflected at about 5 km distance resulting in a 10-km light path length. A telescope focuses the returning light onto the entrance slit of a monochromator the single exit slit of which is replaced by a mechanical scanning device operating at a scan repetition rate of 6.6 KHz. For a typical measurement (1h duration) some 20,000,000 scans are averaged, rendering the contribution of atmospheric turbulence to the spectral noise negligible.

Platt, U.↗
NASA NTRS1980

The lifetime of the OH radical in comets at 1 AU

It has been shown that the photochemical lifetime of OH in comets is a function of the comet's radial velocity. The calculated lifetime at 1 AU can vary between 69,000 and 210,000 sec for radial velocities that vary from -58 to +59 km/sec. A comparison between the scale lengths observed for three comets and those calculated based upon the theoretical lifetime has been made. This comparison shows that in two of the comets the lifetime derived from the scale lengths is a factor of 1.7 larger than the theoretical lifetime. Suggestions are made about the origin of this discrepancy.

Jackson, W. M.↗
NASA NTRS1974

Interactions among the lower valence states of the OH radical

In order to define the origins of experimentally observed predissociations within the A2 sigma/+/ state of OH, overlaps have been computed of the bound level vibrational wavefunctions in the A2 sigma/+/ state with the vibrational continua of states of OH arising from the ground electronic state separated atoms. The dependence of the transition moment upon internuclear distance is derived and compared with previous results. Implications of this analysis in terms of the two body formation of OH are indicated.

Smith, W. H.↗
NASA NTRS2000

Evidence for a Trapped Radical (OH) on Ariel, Oberon, and Titania from Hubble Space Telescope Ultraviolet Spectra

The moons Ariel, Titania, and Oberon have orbits lying within the magnetosphere of Uranus, exposing them to particle irradiation from trapped Ions. This Is similar to the situation experienced by the jovian moons Europa, Ganymede, and Callisto, as well as the saturnian satellites Enceladus, Tethys, Dione, and Rhea. Identification of SO2 on Europa, Ganymede and Callisto, and O3 on Ganymede, Rhea, and Dione has supported suggestions that chemical modifications occur on icy bodies due to ion bombardment associated with the particles entrained within the magnetospheric fields of Jupiter and Saturn. Similar to the Jovian and saturnian satellites mentioned above, water ice is a major component on the larger uranian satellites", thus one might anticipate chemical modification to he an important process in the uranian system. Laboratory studies or the interaction of ultraviolet (uv) and charged-particle radiation with water ice show that in addition to molecular species, a variety of radicals are also produced. We report here evidence for an uv absorption feature in the spectra of Ariel, Titania, and Oberon that we identify as due, in part, to OH; providing the first evidence of a radical produced and trapped on an icy moon within our solar system.

Roush, Ted L.↗
DOE OSTI2020

Experimental and theoretical studies of the doubly substituted methyl-ethyl Criegee intermediate: Infrared action spectroscopy and unimolecular decay to OH radical products

In this work the infrared (IR) action spectrum of the doubly substituted methyl-ethyl Criegee intermediate (MECI) is observed in the CH stretch overtone region with detection of OH products. The MECI exhibits four conformers, all of which undergo unimolecular decay via a 1,4 H-atom transfer mechanism, followed by the rapid release of OH products. Conformers with different orientations of the carbonyl oxide group with respect to the methyl and ethyl substituents (i.e., anti and syn ) decay via distinct transition state barriers (16.1 kcal mol –1 and 15.4 kcal mol –1 , respectively). The observed IR action spectrum is in good agreement with the predicted anharmonic IR absorption spectrum, but exhibits significant congestion, which is attributed to couplings between spectroscopic bright states and nearby dark states. Energy-dependent OH appearance rates are measured upon IR excitation of the strongest features in the IR action spectrum and are found to be on the order of 10 6 –10 7 s –1 . The experimental rates are in good agreement with computed Rice–Ramsperger–Kassel–Marcus rates for the unimolecular decay of MECI at these energies, which incorporate quantum mechanical tunneling and sophisticated hindered rotor treatments, as well as high-level theoretical calculations of the TS barrier heights, rovibrational properties, and torsional barriers associated with the MECI conformers. Master equation modeling is used to predict thermal rates for the unimolecular decay of anti - and syn -MECI of 473 s –1 and 660 s –1 , respectively. Comparison with other previously studied Criegee intermediate systems provides insights into substituent effects on unimolecular decay under both energy-dependent and thermal conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Water Catalysis of the Reaction of Methanol with OH Radical in the Atmosphere is Negligible

Abstract Faced with the contradictory results of two recent experimental studies [Jara‐Toro et al., Angew. Chem. Int. Ed . 2017 , 56 , 2166 and Chao et al., Angew. Chem. Int. Ed . 2019 , 58 , 5013] of the possible catalytic effect of water vapor on CH 3 OH + OH reaction, we report calculations that corroborate the conclusion made by Chao et al. and extend the rate constant evaluation down to 200 K. The rate constants of the CH 3 OH + OH reaction catalyzed by a water molecule are computed as functions of temperature and relative humidity using high‐level electronic structure and kinetics calculations. The Wuhan–Minnesota Scaling (WMS) method is used to provide accurate energetics to benchmark a density functional for direct dynamics. Both high‐frequency and low‐frequency anharmonicities are included. Variational and tunneling effects are treated by canonical variational transition state theory with multidimensional small‐curvature tunneling. And, most significantly, we include multistructural effects in the rate constant calculations. Our calculations show that the catalytic effect of water vapor is not observable at 200–400 K.

Wu, Junjun↗
NASA NTRS1990

Development of a two photon/laser induced fluorescence technique for the detection of atmospheric OH radicals

The development of a new mid-IR laser source was the primary goal. Backward propagating stimulated D2 Raman frequency down conversion of a commercially available 1.06 micron Nd:YAG laser was shown to generate an efficient source of 1.56 micron radiation with near diffraction limited beam quality. The efficient generation of a 2.9 micron laser source was also achieved using backward propagating CH4 Raman frequency down conversion of the 1.56 micron pump. Slightly higher efficiencies were obtained for frequency down conversion of the 1.06 micron Nd:YAG using the H2 Raman shift yielding a near diffraction limited source in the 200 mJ range at 1.9 micron. Similar conversion efficiencies are anticipated as a result of extending the wavelength coverage of recently available Ti:sapphire pulse laser to not only cover the 740 to 860 nm fundamental wavelength range but also the .95 to 1.15 and 1.06 to 1.33 micron range using D2 and H2, respectively. The anticipated sensitivity of a TP-LIF OH sensor using this mid-IR source would give signal limited detection of 1.4 x 10(exp 5) OH/cu cm under boundary layer conditions and 5.5 x 10(exp 4) OH/cu cm under free troposphere sampling conditions for a five minute signal integration period. This level of performance coupled with the techniques non-perturbing nature and freedom from both interferences and background would allow reliable tropospheric OH measurement to be obtained under virtually any ambient condition of current interest, including interstitial and sampling.

Bradshaw, John↗
NASA NTRS1990

The Tropospheric Lifetimes of Halocarbons and Their Reactions with OH Radicals: an Assessment Based on the Concentration of CO-14

Chemical reaction with hydroxyl radicals formed in the troposphere from ozone photolysis in the presence of methane, carbon monoxide and nitrogen oxides provides an important removal mechanism for halocarbons containing C-H and C = C double bonds. The isotropic distribution in atmospheric carbon monoxide was used to quantify the tropospheric hydroxyl radical distribution. Here, this methodology is reevaluated in the light of recent chemical kinetic data evaluations and new understandings gained in the life cycles of methane and carbon monoxide. None of these changes has forced a significant revision in the CO-14 approach. However, it is somewhat more clearly apparent how important basic chemical kinetic data are to the accurate establishment of the tropospheric hydroxyl radical distribution.

Derwent, Richard G.↗
DOE OSTI2020

Verification of diesel spray ignition phenomenon in dual-fuel diesel-piloted premixed natural gas engine

Dual-fuel (DF) engines, in which premixed natural gas and air in an open-type combustion chamber is ignited by diesel-fuel pilot sprays, have been more popular for marine use than pre-chamber spark ignition (PCSI) engines because of their superior durability. However, control of ignition and combustion in DF engines is more difficult than in PCSI engines. In this context, here we focus on the ignition stability of n-heptane pilot-fuel jets injected into a compressed premixed charge of natural gas and air at low-load conditions. To aid understanding of the experimental data, chemical-kinetics simulations were carried out in a simplified engine-environment that provided insight into the chemical effects of methane (CH4) on pilot-fuel ignition. The simulations reveal that CH4 has an effect on both stages of n-heptane autoignition: the small, first-stage, cool-flame-type, low-temperature ignition (LTI) and the larger, second-stage, high-temperature ignition (HTI). As the ratio of pilot-fuel to CH4 entrained into the spray decreases, the initial oxidization of CH4 consumes the OH radicals produced by pilot-fuel decomposition during LTI, thereby inhibiting its progression to HTI. Using imaging diagnostics, the spatial and temporal progression of LTI and HTI in DF combustion are measured in a heavy-duty optical engine, and the imaging data are analyzed to understand the cause of severe fluctuations in ignition timing and combustion completeness at low-load conditions. Images of cool-flame and hydroxyl radical (OH*) chemiluminescence serve as indicators of LTI and HTI, respectively. The cycle-to-cycle and spatial variation in ignition extracted from the imaging data are used as key metrics of comparison. The imaging data indicate that the local concentration of the pilot-fuel and the richness of the surrounding natural-gas air mixture are important for LTI and HTI, but in different ways. In particular, higher injection pressures and shorter injection durations increase the mixing rate, leading to lower concentrations of pilot-fuel more quickly, which can inhibit HTI even as LTI remains relatively robust. Decreasing the injection pressure from 80 MPa to 40 MPa and increasing the injection duration from 500 µs to 760 µs maintained constant pilot-fuel mass, while promoting robust transition from LTI to HTI by effectively slowing the mixing rate. This allows enough residence time for the OH radicals, produced by the two-stage ignition chemistry of the pilot-fuel, to accelerate the transition from LTI to HTI before being consumed by CH4 oxidation. Thus from a practical perspective, for a premixed natural gas fuel–air equivalence-ratio, it is possible to improve the “stability” of the combustion process by solely manipulating the pilot-fuel injection parameters while maintaining constant mass of injected pilot-fuel. This allows for tailoring mixing trajectories to offset changes in fuel ignition chemistry, so as to promote a robust transition from LTI to HTI by changing the balance between the local concentration of the pilot-fuel and richness of the premixed natural gas and air. This could prove to be a valuable tool for combustion design to improve fuel efficiency or reduce noise or perhaps even reduce heat-transfer losses by locating early combustion away from in-cylinder walls.

42 ENGINEERING↗
DOE OSTI2023

Direct Conversion of Ethane to Oxygenates, Ethylene, and Hydrogen in a Noncatalytic Biphasic Plasma Microreactor

We selectively upgrade ethane (C 2 H 6 ) to ethanol (C 2 H 5 OH), methanol (CH 3 OH), and acetic acid (CH 3 COOH) in a catalyst-free, continuous, argon/water biphasic plasma microreactor. The water (H 2 O) evaporates and electron- dissociates into OH· radicals. OH· recombines with alkyl radicals, produced via electron dissociation of ethane, to generate the oxygenates that absorb into H 2 O. A plasma-assisted path, reminiscent of the low-temperature thermocatalytic ethane steam reforming, leads to significant H 2 coproduction. The gaseous stream also comprises CO 2 and C 2 H 4 . Up to 1.3 and 1 μmol min –1 of liquid C 2 H 5 OH and CH 3 OH are attained, respectively. Compared to CO 2 -assisted ethane plasma conversion, which produces many oxygenates with low selectivity, the carbon selectivity can range from >70% C 2 H 5 OH, CH 3 OH, and CH 3 COOH to 60% C 2 H 4 . Furthermore, the low carbon footprint, electrified, modular, intensified process using a reactive evaporation and separation plasma could pave the way for the valorization of underutilized shale gas resources in remote areas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1992

Simultaneous temperature and multispecies measurement in a lifted hydrogen diffusion flame

UV spontaneous vibrational Raman scattering and laser-induced predissociative fluorescence (LIPF) techniques are combined and applied to a lifted hydrogen jet diffusion flame. Simultaneous, temporally and spatially resolved point measurements of temperature, major species concentrations (H2, O2, N2, H2O), and absolute hydroxyl radical concentration (OH) are obtained with a 'single' excimer laser for the first time. For OH measurements, the use of LIPF makes quenching corrections unnecessary. Results demonstrate that fuel and oxidizer are in a rich, premixed, and unignited condition in the center core of the lifted flame base. In the lifted zone, combustion occurs in an intermittent annular turbulent flame brush and strong finite-rate chemistry effects result in nonequilibrium values of temperature, major species, and OH radicals. Downstream in the slow three-body recombination zone, the major species concentrations are in partial equilibrium, the OH concentrations are in superequilibrium, and the temperatures are in subequilibrium. Far downstream in the flame, equilibrium values of temperature, OH radical, and major species are found.

Cheng, T. S.↗
NASA NTRS1988

Tropospheric nitric oxide measurements

Nitric oxide (NO) plays a key role in tropospheric photo-chemistry. The photochemical oxidation of hydrocarbons, for example, can serve as either a source or a sink for ozone, depending on the local abundance of NO. Nitric oxide also helps govern atmospheric concentrations of the hydroxyl (OH) radical. The OH radical is the single most important player in photochemical transformations because it controls the atmospheric lifetimes of so many chemical species. Although NO serves as a very effective catalyst in many important chemical processes, its concentration is low enough to normally be expressed in units of parts per trillion by volume (pptv). Consequently, commercially available detectors for NO (with detection limits of about one part per billion) have proven to be unsuitable for use anywhere except in urban areas and near other local pollution sources. Under the sponsorship of NASA's Global Tropospheric Experiment (GTE), Wallops has developed an extremely sensitive detector with a detection limit of a few pptv. The system was specifically designed for aircraft use, with the objective of applying it in global aircraft studies of tropospheric chemistry. Studies with the detector are examined.

Torres, A. L.↗
NASA NTRS1973

Reactions of HO2 with carbon monoxide and nitric oxide and of O/1 D/ with water.

Investigation of the reactions of the hydroperoxyl radical with carbon monoxide and nitric oxide in a static system, and reexamination of the reaction of O(1 D) with water. The HO2 radicals were generated by the photolysis of N2O at 2139 A in the presence of excess H2O or H2 and smaller amounts of CO and O2. The O(1 D) atoms produced from the photolysis of N2O react with H2O or with H2 to give OH radicals in the case of H2O or OH radicals and H atoms in the case of H2. With H2O, two OH radicals are produced for each O(1 D) removed at low pressures, but the OH yield drops as the pressure is raised. This drop is attributed to an insertion reaction which removes from 10 to 30% of the O(1 D) atoms at about 650 torr of H2O at 200 F. The OH radicals generated can react with either CO or H2 to produce H atoms, which then add to O2 to produce HO2. In the absence of NO, the HO2 radicals could react by two routes, while with NO present NO2 is produced in a long chain process.

Simonaitis, R.↗