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All sourcesNASA NTRSDOE OSTI
NASA NTRS2006

H2 Detection via Polarography

Polarography is the measurement of the current that flows in solution as a function of an applied voltage. The actual form of the observed polarographic current depends upon the manner in which the voltage is applied and on the characteristics of the working electrode. The new gas polarographic H2 sensor shows a current level increment with concentration of the gaseous H2 similar to those relating to metal ions in liquid electrolytes in well-known polarography. This phenomenon is caused by the fact that the diffusion of the gaseous H2 through a gas diffusion hole built in the sensor is a rate-determining step in the gaseous-hydrogen sensing mechanism. The diffusion hole artificially limits the diffusion of the gaseous H2 toward the electrode located at the sensor cavity. This gas polarographic H2 sensor is actually an electrochemical-pumping cell since the gaseous H2 is in fact pumped via the electrochemical driving force generated between the electrodes. Gaseous H2 enters the diffusion hole and reaches the first electrode (anode) located in the sensor cavity to be transformed into an H ions or protons; H ions pass through the electrolyte and reach the second electrode (cathode) to be reformed to gaseous H2. Gas polarographic O2 sensors are commercially available; a gas polarographic O2 sensor was used to prove the feasibility of building a new gas polarographic H2 sensor.

Dominquez, Jesus↗
NASA NTRSDate not supplied

Some NASA Perspectives on H2

This presentation provides the NASA perspective for government and industry technology developers world-wide who are exploring the potential for hydrogen (H2) in aviation applications including electric aircraft, airport vehicles, and airport related equipment. NASA’s H2 interest has been related to vehicle-level technology development and integration only, but NASA is keenly aware of the necessity of work focused on solving the challenges of H2 airport infrastructure. Some historical perspectives are provided on NASA efforts in H2 fuel cell development for space and aeronautics applications. NASA’s current research portfolio includes some investigation of H2 energy storage and hydrocarbon conversion for fuel cells on electric aircraft. There is no current emphasis on the other H2-related challenges. Over the years NASA has conducted research into “Quiet Green Transport” with a H2 fuel cell powered aircraft, an Emissionless Aircraft Study with Non Flow Through – Regenerative Fuel Cell (NFT-RFC) technology which captures the water, and an H2 fuel cell powered Unmanned Aerial Vehicle (UAV) study. NASA has flown a long endurance UAV using a RFC in the Low Emissions Alternative Power (LEAP) program. Recently, NASA conducted feasibility studies on hybrid SOFC with onboard hydrocarbon fuel reformation for aircraft primary propulsive power and secondary power under the Fostering Ultra-Efficient, Low-Emitting Aviation Power (FUELEAP) program. NASA currently has a multiyear program with the Center for Cryogenic High-Efficiency Electrical Technologies for Aircraft (CHEETA) to explore the benefits of using cryogenic H2 on aircraft for fuel cell propulsion and to provide superconductivity in electrical power management on the aircraft.

Power↗
NASA NTRS1998

Infrared Space Observatory Observations of Molecular Hydrogen in HH 54: Measurement of a Nonequilibrium Ratio of Ortho- to Para-H2

We have detected the S(1), S(2), S(3), S(4), and S(5) pure rotational lines of molecular hydrogen toward the outflow source HH 54 using the Short Wavelength Spectrometer on board the Infrared Space Observatory. The observed H2 line ratios indicate the presence of warm molecular gas with an H2 density of at least 10(sup 5) /cc and a temperature approximately 650 K in which the ratio of ortho- to para-H2 is only 1.2 -+ 0.4, significantly smaller than the equilibrium ratio of 3 expected in gas at that temperature. These observations imply that the measured ratio of ortho- to para-H2 is the legacy of an earlier stage in the thermal history of the gas when the gas had reached equilibrium at a temperature approximately 90 K. Based upon the expected timescale for equilibration, we argue that the nonequilibrium ratio of ortho- to para-H2 observed in HH 54 serves as a chronometer that places a conservative upper limit of approximately 5000 yr on the period for which the emitting gas has been warm. The S(2)/,S(l) and S(3)/S(1) H2 line ratios measured toward HH 54 are consistent with recent theoretical models of Timmermann for the conversion of para- to ortho-H2 behind slow, C-type shocks, but only if the preshock ratio of ortho- to para-H2 was approximately < 0.2.

Neufeld, David A.↗
NASA NTRS1999

The Ratio of Ortho- to Para-H2 in Photodissociation Regions

We discuss the ratio of ortho- to para-H2 in photodissociation regions (PDRs). We draw attention to an apparent confusion in the literature between the ortho-to-para ratio of molecules in FUV-pumped vibrationally excited states and the total H2 ortho-to-para abundance ratio. These ratios are not the same because the process of FUV pumping of fluorescent H2 emission in PDRs occurs via optically thick absorption lines. Thus gas with an equilibrium ratio of ortho- to para-H2 equal to 3 will yield FUV-pumped vibrationally excited ortho-to-para ratios smaller than 3, because the ortho-H2 pumping rates are preferentially reduced by optical depth effects. Indeed, if the ortho and para pumping lines are on the "square root" part of the curve of growth, then the expected ratio of ortho and para vibrational line strengths is 3(sup 1/2) approximately 1.7, close to the typically observed value. Thus, contrary to what has sometimes been stated in the literature, most previous measurements of the ratio of ortho- to para-H2 in vibrationally excited states are entirely consistent with a total ortho-to-para ratio of 3, the equilibrium value for temperatures greater than 200 K. We present an analysis and several detailed models that illustrate the relationship between the total ratios of ortho- to para-H2 and the vibrationally excited ortho-to-para ratios in PDRs. Recent Infrared Space Observatory measurements of pure rotational and vibrational H2 emissions from the PDR in the star-forming region S140 provide strong observational support for our conclusions.

Sternberg, Amiel↗
NASA NTRS1998

Infrared Space Observatory Observations of Molecular Hydrogen in HH 54: Measurement of a Nonequilibrium Ratio of Ortho- to Para-H2

We have detected the S(1), S(2), S(3), S(4), and S(5) pure rotational lines of molecular hydrogen toward the outflow source HH 54 using the Short Wavelength Spectrometer on board the Infrared Space Observatory. The observed H2 line ratios indicate the presence of warm molecular gas with an H2 density of at least 10(exp 5) cm(exp -3) and a temperature approximately 650 K in which the ratio of ortho- to para-H2 is only 1.2 +/- 0.4, significantly smaller than the equilibrium ratio of 3 expected in gas at that temperature. These observations imply that the measured ratio of ortho- to para-H2 is the legacy of an earlier stage in the thermal history of the gas when the gas had reached equilibrium at a temperature approximately less than 90 K. Based upon the expected timescale for equilibration, we argue that the nonequilibrium ratio of ortho- to para-H2 observed in HH 54 serves as a chronometer that places a conservative upper limit of approximately 5000 yr on the period for which the emitting gas has been warm. The S(2)/S(1) and S(3)/S(1) H2 line ratios measured toward HH 54 are consistent with recent theoretical models of Timmermann for the conversion of para- to ortho-H2 behind slow, C-type shocks, but only if the preshock ratio of ortho- to para-H2 was approximately less than 0.2.

Neufeld, David A.↗
NASA NTRS2001

H2 cycling and microbial bioenergetics in anoxic sediments

The simple biochemistry of H2 is central to a large number of microbial processes, affecting the interaction of organisms with each other and with the environment. In anoxic sediments, the great majority of microbial redox processes involve H2 as a reactant, product, or potential by-product, and the thermodynamics of these processes are thus highly sensitive to fluctuations in environmental H2 concentrations. In turn, H2 concentrations are controlled by the activity of H2-consuming microorganisms, which efficiently utilize this substrate down to levels which correspond to their bioenergetic limitations. Consequently, any environmental change which impacts the thermodynamics of H2-consuming organisms is mirrored by a corresponding change in H2 concentrations. This phenomenon is illustrated in anoxic sediments from Cape Lookout Bight, NC, USA: H2 concentrations are controlled by a suite of environmental parameters (e.g., temperature, sulfate concentrations) in a fashion which can be quantitatively described by a simple thermodynamic model. These findings allow us to calculate the apparent minimum quantity of biologically useful energy in situ. We find that sulfate reducing bacteria are not active at energy yields below -18 kJ per mole sulfate, while methanogenic archaea exhibit a minimum close to -10 kJ per mole methane.

Hoehler, Tori M.↗
NASA NTRS2004

Quantitative Relationships between Photosynthetic, Nitrogen Fixing, and Fermentative H2 Metabolism in a Photosynthetic Microbial Mat

The ultimate potential of any microbial ecosystem to contribute chemically to its environment - and therefore, to impact planetary biogeochemistry or to generate recognizable biosignatures - depends not only on the individual metabolic capabilities of constituent organisms, but also on how those capabilities are expressed through interactions with neighboring organisms. This is particularly important for microbial mats, which compress an extremely broad range of metabolic potential into a small and dynamic system. H2 participates in many of these metabolic processes, including the major elemental cycling processes of photosynthesis, nitrogen fixation, sulfate reduction, and fermentation, and may therefore serve as a mediator of microbial interactions within the mat system. Collectively, the requirements of energy, electron transfer, and biomass element stoichiometry suggest quantitative relationships among the major element cycling processes, as regards H2 metabolism We determined experimentally the major contributions to 32 cycling in hypersaline microbial mats from Baja California, Mexico, and compared them to predicted relationships. Fermentation under dark, anoxic conditions is quantitatively the most important mechanism of H2 production, consistent with expectations for non-heterocystous mats such as those under study. Up to 16% of reducing equivalents fixed by photosynthesis during the day may be released by this mechanism. The direct contribution of nitrogen fixation to H2 production is small in comparison, but this process may indirectly stimulate substantial H2 generation, by requiring higher rates of fermentation. Sulfate reduction, aerobic consumption, diffusive and ebulitive loss, and possibly H2-based photoreduction of CO2 serve as the principal H2 sinks. Collectively, these processes interact to create an orders-of-magnitude daily variation in H2 concentrations and fluxes, and thereby in the oxidation-reduction potential that is imposed on microbial processes occuring within the mat matrix.

Hoehler, Tori M.↗
DOE OSTI2024

Milestone 1.2.16. Reconciling the Impacts of Thermal Pretreatment on Radiation-Induced H2 Generation from Aluminum-Clad Spent Nuclear Fuel Surrogate Materials

To support the technical basis for the extended dry storage of aluminum-clad spent nuclear fuel (ASNF), thermal pretreatment procedures to minimize the radiation-induced generation of molecular hydrogen (H2) have been investigated. The aim of thermal pretreatment is to eliminate the residual adsorbed water content on the ASNF’s corrosion layers, precursors for H2 generation. To date, irradiation studies in this area have found conflicting results for the effectiveness of thermal pretreatment procedures. The aim of this study was to reconcile those differences. However, the presented results, which utilized a modified in situ thermal pretreatment procedure, afforded H2 yield data that further indicates that thermal pretreatment does not significantly reduce the radiation-induced yield of H2 from gamma irradiated ASNF surrogate materials. Assessment of the differences between thermal pretreatment studies suggests that stainless-steel—present in the irradiation setup of studies that demonstrated a reduction in the yield of H2 with thermal pretreatment—may afford not only unanticipated interfacial chemistry, but also the formation and radiolytic contribution of iron oxides to the chemistry underpinning the formation of H2 in these systems. Given the Department of Energy Standard Canister—proposed for the extended dry storage of ASNF—is predominantly composed of stainless-steel, the potential contribution of stainless-steel and its corrosion layers to radiolytic H2 production should be further investigated. This research was funded by the U.S. Department of Environmental Management, Office of Technology Development, under contract DE-AC07-05ID14517.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2026

The anaerobic fungus Caecomyces churrovis produces H2 via a non-3 bifurcating NADH-dependent enzyme complex

Anaerobic fungi (AF) decompose lignocellulose-based biomass into fermentable sugars through the production of powerful biomass-degrading enzymes. AF are unusual among fungi in that they generate energy via hydrogenosomes, which are also associated with the release of H2 though yet unknown metabolic mechanisms. In particular, it remains unclear how NAD(P)+ is regenerated within hydrogenosomes and how H2 is formed. Here, we reveal the molecular mechanism for hydrogenosomal H2 production in the AF strain C. churrovis by combining genomic search, proteomic analysis, and enzymology. Our enzyme assays on the large organelle fraction of C. churrovis revealed the activity of H2:NAD+ oxidoreductase but not pyruvate:ferredoxin oxidoreductase activity. We identified genes encoding [FeFe] hydrogenase (Hyd) and NADH dehydrogenase subunits E and F (NuoE, NuoF) in C. churrovis, and confirmed their expression in the isolated hydrogenosomal fractions by proteomic analysis. Combining the individually purified proteins, we found that the assay system consisting of Hyd-Strep and NuoEF-Strep reduced NAD+ with H2. Furthermore, this system formed H2 directly from NADH independent of ferredoxin, functioning as a non-bifurcating NADH-dependent enzyme rather than an electron-bifurcating enzyme. We identified homologs of hydrogenosomal NuoE, NuoF, and Hyd in many other AF, indicating this pathway is widely conserved among the early-branching AF. This work demonstrates the existence of a non-bifurcating NADH-dependent enzyme complex in eukaryotes. Moreover, this complex could be a target for controlling AF H2 production and altering fungal metabolism.

fungi↗
NASA NTRS1974

Neptune - Observations of the H2 quadrupole lines in the /4-0/ band

The first measurement of Neptune's quadrupole H2 lines is reported. The equivalent widths of the S(0) and S(1) lines of the (4-0) band are given along with the corresponding widths measured from comparison spectra of Uranus taken on the same nights. These are interpreted in terms of both an inhomogeneous atmosphere overlying a reflecting layer and a homogeneous, semi-infinite, scattering atmosphere. Only the scattering model proves to be consistent with Neptune's spectrum in this wavelength region. The H2 abundance along the scattering mean free path is found to be less than the value for Rayleigh scattering in pure H2. This result is interpreted in terms of the presence of H2, CH4, and at least one other gas, instead of the more conventional interpretation in terms of the presence of an aerosol mixed with H2. Weak features in the continuum were observed. Their widths and the strength of the H2 features indicate that H2 is more abundant than the sum of the remaining gases in these atmospheres.

Trafton, L.↗
NASA NTRS1978

H2 cooling, dissociation, and infrared emission in shocked molecular clouds

Models are presented of interstellar shocks in molecular clouds over ranges of ambient molecular density from 1000 to 10 million per cu cm and shock velocity from 6 to 14 km/s. Estimates of H2-H2 collisional-excitation rates are used to derive the H2 radiative cooling rates from vibrational-rotational quadrupole transitions as a function of n(H2) and temperature. The emissivities integrated through the shock of the strongest infrared lines in the v = 1-0, 2-0, and 2-1 bands of H2. The effectiveness of H2 dissociative cooling is considered for the highest-velocity shocks. The H2 line intensities from such shocks are compared with those produced by the 'competitive' mechanism of UV pumping for two likely driving mechanisms of shocks - wind-driven shells and expanding H II regions.

Shull, J. M.↗
NASA NTRS1995

Hopkins Ultraviolet Telescope observations of H2 toward the planetary nebula NGC 1535

We have observed the far-ultraviolet spectrum (912-1860 A) of the bright high-excitation planetary nebula NGC 1535 with approximately 3 A resolution using the Hopkins Ultraviolet Telescope (HUT) aboard the Astro-1 space shuttle pmission in 1990 December. We see strong continuum emission down to the Lyman limit and strong P Cygni profiles from high-excitation lines such as C IV wavelength 1549, N V wavelength 1240, O V wavelength 1371, and O VI wavelength 1035. Below 1150 A strong absorption bands of H2 are seen, which were unanticipated by us because of the low reddening and high galactic latitude of the object and the absence of detected H2 emission in the infrared. We construct model H2 spectra and convolve them to the HUT resolution for comparison with the NGC 1535 data. We find good agreement with a population distribution characterized by a single temperature (T = 300 K) or a two-temperature model (T = 144/500 K), and determine limits on the H2 column density. While both inter-stellar and circumstellar origins for the observed H2 absorption are plausible, we ascribe the material to the planetary nebula in order to estimate the conditions of excitation and place upper limits on the mass of both H2 and H1 in this system. Because the UV transitions are ground-state connected, we determine a stringent upper limit of 0.03 d(sup 2)(sub 1.6) solar mass on the mass of H2, where d(sub 1.6) is the distance relative to an assumed distance of 1.6 kpc. This value is less model-dependent than IR estimates. Along with the central star and nebular masses, these estimates allow us to limit the main-sequence mass of the progenitor star to less than 1.8 solar mass. This upper limit is consistent with a relatively low-mass extended thick disk or Population II progenitor, as expected for an object approximately 1 kpc off the galactic plane.

Bowers, Charles W.↗
NASA NTRS1995

Structure of V(H2)n(+) Clusters for n = 1-6

Geometries, vibrational frequencies, spin states, H2 binding energies, and Delta(S) values have been determined for V(H2)n(+), for n = 1-6, using the B3LYP hybrid functional. The binding energies and Delta(S) values are in good agreement with experiment, thus showing that the B3LYP functional offers a reliable approach for optimizing the geometry and determining the H2 binding energies for this system. The calculations show that the increase in the binding energy and entropy associated with the addition of the sixth H2 to V(+) is due to a change in spin state from quintet for the smaller clusters to triplet for V(H2)6(+). The results for V(H2)n(+) are compared with those for CO(H2)n(+).

Maitre, Philippe↗
NASA NTRS1996

Rate Coefficients of C2H with C2H4, C2H6, and H2 from 150 to 359 K

Rate coefficients for the reactions C2H with C2H4, C2H6, and H2 are measured over the temperature range 150-359 K using transient infrared laser absorption spectroscopy. The ethynyl radical is formed by photolysis of C2H2 with a pulsed excimer laser at 193 nm, and its transient absorption is monitored with a color center laser on the Q(sub 11)(9) line of the A(sup 2) Pi-Chi(sup 2) Sigma transition at 3593.68 cm(exp -1). Over the experimental temperature range 150-359 K the rate constants of C2H with C2H4, C2H6, and H2 can be fitted to the Arrhenius expressions k(sub C2H4) = (7.8 +/- 0.6) x 10(exp -11) exp[(134 +/- 44)/T], k(sub C2H6) = (3.5 +/- 0.3) x 10(exp -11) exp[(2.9 +/- 16)/T], and k(sub H2) = (1.2 +/- 0.3) x 10(exp -11) exp[(-998 +/- 57)]/T cm(exp 3) molecule(exp -1) sec(exp -1). The data for C2H with C2H4 and C2H6 indicate a negligible activation energy to product formation shown by the mild negative temperature dependence of both reactions. When the H2 data are plotted together with the most recent high-temperature results from 295 to 854 K, a slight curvature is observed. The H2 data can be fit to the non-Arrhenius form k(sub H2) = 9.2 x 10(exp -18) T(sup 2.17 +/- 0.50) exp[(-478 +/- 165)/T] cm(exp 3) molecules(exp -1) sec(exp -1). The curvature in the Arrhenius plot is discussed in terms of both quantum mechanical tunneling of the H atom from H2 to the C2H radical and bending mode contributions to the partition function.

Opansky, Brian J.↗
NASA NTRS1977

Saturn - Long-term variation of H2 and CH4 absorptions

Results are presented for observations of various H2 quadrupole lines and CH4 absorption bands in spectra of Saturn obtained with a coude scanner at each apparition since 1969. The data are found to indicate a long-term variation in Saturn's H2 equivalent widths, a seasonal dependence of H2 line strength, and a fairly steady increase in CH4 absorption during the period from 1973 to 1976. A possible correlation between planetary shading and the strength of H2 absorption features is discussed along with seasonal variations in Saturn's NH3 cloud deck and atmospheric models that correspond to the observed H2 equivalent widths. It is suggested that: (1) significant shadowing by the rings may cause dynamical atmospheric activity due to the occurrence of a temperature gradient in the penumbral boundaries of the ring shadow in the planet's upper atmosphere; (2) cooling in the shadow may be a source of a high-altitude CH4 mist; and (3) spreading of this mist over the globe by advective winds would reduce the H2 and CH4 absorptions, as observed.

Trafton, L.↗
NASA NTRS1981

H2 abundance in the atmosphere of Venus

The in situ measurements from the Pioneer Venus Orbiter (PVO) Ion Mass Spectrometer have led to the detection of H2(+) ions in the Venus ionosphere. Although H2(+) is a minor ion, its measurement provides the first direct clue for determining the H2 abundance in the upper atmosphere of Venus. A photochemical model using PVO measurements is used to derive an H2 mixing ratio of 10 ppm below 140 km altitude. The presence of this much H2 confirms a previous prediction that the reactions of O(+) with H2 and subsequent recombination of OH(+) provide an important source of nonthermal H observed in the Venus atmosphere. The estimated escape flux for H is 10 to the 8th per sq cm/s.

Kumar, S.↗
NASA NTRS1987

Measurement and analysis of the far infrared absorption spectrum of the gaseous mixture H2-CH4

The collision-induced absorption of H2-CH4 mixtures was measured from 20 to 900/cm at 195 and 297 K. By subtracting the absorption due to H2-H2 and CH4-CH4 collisions from that of the mixture, the absorption due to H2-CH4 collisions was obtained. This spectrum was analyzed using the BC model line shape to provide a way of estimating the far-IR spectrum of H2-CH4 for various concentrations of H2 and CH4. Theoretical spectral moments were computed with different potential functions and compared with experimental values.

Birnbaum, George↗
NASA NTRS1990

The 3.3 micron feature, H2, and ionized gas in the Orion bar

The results of spectroscopy of the 3.3 micron feature, H2 emission, P-alpha, and Br-alpha, obtained along a line perpendicular to the Orion ionization front, are presented. The intensity of the 3.3 micron feature reaches a maximum between the ionization front and the H2 peak. The 3.33 micron spatial distribution appears to be due to destruction of the emitting material within the H II region and extinction of the exciting radiation between the edge of the H II region and the H2 peak, resulting in a maximum between the ionization front and the H2 peak. The H2 peak is consistent with either being due to a shock front or being due to UV-pumped fluorescence from dense clumps of H2. The width of the 3.3 micron feature observed at high spectral resolution is constant in regions of varying UV flux. It is suggested that the strength of the UV field is not the cause of the variations in the 3.3 micron feature width observed in other sources, but rather that these variations are caused by a compositional change related to the age of the emitting material.

Sellgren, K.↗