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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
NASA NTRS1991

Kinetic conversion of CO to CH4 in the Solar System

Some of the most interesting chemistry in the Solar System involves changes in the oxidation state of the simple carbon species. The chemical pathways for the conversion of CH4 to CO and CO2 are for the most part known. The reverse process, the reduction of CO to CH4, is, however, poorly understood. This is surprising in view of the importance of the reduction process in the chemistry of the Solar System. Recently we investigated the chemical kinetics of a hitherto unsuspected reaction. It is argued that the formation of the methoxy radical (CH3O) from H+H2CO may play an essential role in the reduction of CO to CH4. The rate coefficient for this reaction has been estimated using the approximate theory of J. Troe and transition state theory. We will discuss the implications of this reaction for the chemistry of CO on Jupiter, in the solar nebula, for interpreting the laboratory experiments of A. Bar-Nun and A. Shaviv and A. Bar-Nun and S. Chang, and for organic synthesis in the prebiotic terrestrial atmosphere. The possible relation of CO reduction in the solar nebula and polyoxymethylene observed in comet Halley will be discussed.

Yung, Y. L.↗
NASA NTRS1992

In situ stratospheric measurements of CH4, (C-13)H4, N2O, and OC(O-18) using the BLISS tunable diode laser spectrometer

Simultaneous in situ measurements of stratospheric CH4, (C-13)H4, N2O, OC(O-18), pressure, and temperature have been made from Palestine, Texas (32 deg N) in September 1988 with the JPL Balloon-borne Laser In Situ Sensor. Measurements of CH4 and N2O in the altitude range 30-35 km agree well with other measurements, except for an anomalously high value for the N2O at 31 km. Measurements of CH4 support earlier observations of fold in the vertical profile. A ratio for stratospheric (C-13)H4/CH4 of 0.0105 +/- 0.0010 implies an enrichment of delta(C-13) = -45 +/- 92 parts per thousand over the PDB value, in agreement with previous measurements in the troposphere. A large mixing ratio of 1.9 +/- 0.2 ppmv for OC(O-18) is measured, corresponding to an enrichment of delta(O-18) = 280 +/- 50 parts per thousand for the (O-18) isotopic species over the SMOW value.

Webster, Christopher R.↗
NASA NTRS1992

Observation of intense Stokes and anti-Stokes lines in CH4 pumped by 355 nm of a Nd:YAG laser

The stimulated Raman scattering (SRS) and four-wave mixing (FWM) processes are studied in detail in CH4 gas pumped by the third-harmonic of Nd:YAG laser at 355 nm. The conversion efficiency and average output energy are measured for the various Stokes and anti-Stokes lines at different experimental conditions. The threshold input energy at various CH4 pressures is calculated for the unguided and capillary waveguide Raman cells. The calculated values for the capillary case are compared with the measured values at different CH4 pressures and the two results are in good agreement.

Sentrayan, K.↗
NASA NTRS1993

The atmospheric CH4 increase since the Last Glacial Maximum. I - Source estimates

An estimate of the distribution of wetland area and associated CH4 emission is presented for the Last Glacial Maximum (LGM, 18 kyr BP, kiloyear Before Present) and the Pre-Industrial Holocene (PIH, 9000-200 years BP). The wetland source, combined with estimates of the other biogenic sources and sink, yields total source strengths of 120 and 180 Tg CH4/yr for LGM and PIH respectively. These source strengths are shown to be consistent with source estimates inferred from a photochemical model, and point to changes in wetland CH4 source as a major factor driving the atmospheric CH4 increase from LGM to PIH.

Chappellaz, Jerome A.↗
NASA NTRS1995

An Accurate ab initio Quartic Force Field and Vibrational Frequencies for CH4 and Isotopomers

A very accurate ab initio quartic force field for CH4 and its isotopomers is presented. The quartic force field was determined with the singles and doubles coupled-cluster procedure that includes a quasiperturbative estimate of the effects of connected triple excitations, CCSD(T), using the correlation consistent polarized valence triple zeta, cc-pVTZ, basis set. Improved quadratic force constants were evaluated with the correlation consistent polarized valence quadruple zeta, cc-pVQZ, basis set. Fundamental vibrational frequencies are determined using second-order perturbation theory anharmonic analyses. All fundamentals of CH4 and isotopomers for which accurate experimental values exist and for which there is not a large Fermi resonance, are predicted to within +/- 6 cm(exp -1). It is thus concluded that our predictions for the harmonic frequencies and the anharmonic constants are the most accurate estimates available. It is also shown that using cubic and quartic force constants determined with the correlation consistent polarized double zeta, cc-pVDZ, basis set in conjunction with the cc-pVQZ quadratic force constants and equilibrium geometry leads to accurate predictions for the fundamental vibrational frequencies of methane, suggesting that this approach may be a viable alternative for larger molecules. Using CCSD(T), core correlation is found to reduce the CH4 r(e), by 0.0015 A. Our best estimate for r, is 1.0862 +/- 0.0005 A.

Lee, Timothy J.↗
NASA NTRS2013

Air- and Self-Broadened Half Widths, Pressure-Induced Shifts, and Line Mixing in the Nu(sub 2) Band of (12)CH4

Lorentz self- and air-broadened half width and pressure-induced shift coefficients and their dependences on temperature have been measured from laboratory absorption spectra for nearly 130 transitions in the nu(sub 2) band of (12)CH4. In addition line mixing coefficients (using the relaxation matrix element formalism) for both self- and airbroadening were experimentally determined for the first time for a small number of transitions in this band. Accurate line positions and absolute line intensities were also determined. These parameters were obtained by analyzing high-resolution (approx. 0.003 to 0.01 per cm) laboratory spectra of high-purity natural CH4 and air-broadened CH4 recorded at temperatures between 226 and 297 K using the McMath-Pierce Fourier transform spectrometer (FTS) located at the National Solar Observatory on Kitt Peak, Arizona. A multispectrum nonlinear least squares technique was used to fit short (5-15 per cm) spectral intervals in 24-29 spectra simultaneously. Parameters were determined for nu(sub 2) transitions up to J" = 16. The variations of the measured broadening and shift parameters with the rotational quantum number index and tetrahedral symmetry species are examined. The present results are also compared with previous measurements available in the literature.

Smith, M. A. H.↗
NASA NTRS2020

Probing the Evolutionary History of Comets: an Investigation of the Hypervolatiles CO, CH4, and C2H6 in the Jupiter-Family Comet 21P/Giacobini–Zinner

Understanding the cosmogonic record encoded in the parent volatiles stored in cometary nuclei requires investigating whether evolution (thermal or otherwise) has modified the composition of short-period comets during successive perihelion passages. As the most volatile molecules systematically observed in comets, the abundances of CO, CH4, and C2H6 in short-period comets may serve to elucidate the interplay between natal conditions and post-formative evolution in setting present-day composition, yet secure measurements of CO and CH4 in Jupiter-family comets (JFCs) are especially sparse. The highly favorable 2018 apparition of JFC 21P/Giacobini–Zinner enabled a sensitive search for these "hypervolatiles" in a prototypical carbon-chain depleted comet. We observed 21P/Giacobini–Zinner with the iSHELL spectrograph at the NASA Infrared Telescope Facility on four pre-perihelion dates, two dates near-perihelion, and one post-perihelion date. We obtained detections of CO, CH4, and C2H6 simultaneously with H2O on multiple dates. We present rotational temperatures, production rates, and mixing ratios. Combined with previous work, our results may indicate that the hypervolatile coma composition of 21P/Giacobini–Zinner was variable across apparitions as well as within a particular perihelion passage, yet the spread in these measurements is a relatively small fraction of the variation in each molecule from comet to comet. We discuss the implications of our measured hypervolatile content of 21P/Giacobini–Zinner for the evolution of JFCs, and place our results in the context of findings from the Rosetta mission and ground-based studies of comets.

Roth, Nathan X.↗
NASA NTRS1972

Phase equilibria in fluid mixtures at high pressures - The He-CH4 system.

An experimental study of phase equilibria in the He-CH4 system has been carried out over the temperature range 95 to 290 K and at pressures to 10,000 atm. The experimental results consist of equilibrium phase composition for twenty-eight isotherms in the region of coexistence of two fluid phases, together with the pressure-temperature trace of the three-phase boundary at which a CH4-rich solid phase is in equilibrium with the two fluid phases. The system exhibits a fluid-fluid phase separation which persists to temperatures and pressures beyond the range of this experiment. These findings are relevant to problems of deep atmosphere and interior structures in the outer planets.-

Streett, W. B.↗
NASA NTRS1972

Phase equilibria in fluid mixtures at high pressures: The He-CH4 system

An experimental study of phase equilibria in the He-CH4 system was carried out over the temperature range 95 to 290 K and at pressures to 10,000 atm. The experimental results consist of equilibrium phase composition for twenty-eight isotherms in the region of coexistence of two fluid phases, together with the pressure-temperature trace of the three-phase boundary at which a CH4-rich solid phase is in equilibrium with the two fluid phases. The system exhibits a fluid-fluid phase separation which persists to temperatures and pressures beyond the range of this experiment. These results, together with those recently obtained for other binary systems, provide information about the form of phase diagrams for binary gas mixtures in the region of pressure induced phase transitions at high pressures. These findings are relevant to problems of deep atmosphere and interior structures in the outer planets.

Streett, W. B.↗
NASA NTRS1974

A search for H2O and CH4 in Comet Kohoutek

A spectroscopic search for H2O and CH4 in Comet Kohoutek (1973f) was made using a Pepsios interferometer. No evidence was found for either molecule, allowing to set an upper limit on their production rates (on about Jan. 21, 1974) of Q(H2O) less than 6.2 times 10 to the 28th power per sec and Q(CH4) less than 20 times 10 to the 30th power per sec.

Traub, W. A.↗
NASA NTRS1975

Shock tube measurements of specific reaction rates in the branched chain CH4-CO-O2 system

Growth constants, obtained by measuring the blue CO flame band emission behind incident shock waves, were obtained for two elementary bimolecular reactions involved in the oxidation of methane. Gas mixtures containing small amounts of CH4 with varying amounts of CO, O2, and in one case CO2, diluted with argon, were investigated, and exponential growth constants were derived from plots of the logarithm of observed light intensity versus gas time. The rate constant for the reaction O + CH4 yields CH3 + OH was found to be 1.9 times 10 to the 14th exp(-5900/T) cu cm per mole per sec in the range 1300-2000 K; for the reaction CH3 + O2 yields CH3O + O, the rate constant was determined to be 2.4 times 10 to the 13th exp(-14,500/T) cu cm per mole per sec in the range 1200 to 1900 K.

Brabbs, T. A.↗
NASA NTRS1976

Interactions of CH4 and CO in the earth's atmosphere

Global distributions, sources, and sinks of methane and carbon monoxide in upper and lower levels of the earth's atmosphere, and the global budgets of methane and carbon monoxide, are studied, with emphasis on cumulative pollution. Stratospheric contents, vertical profiles of concentrations, simulation of vertical transport through the atmosphere, and latitudinal distributions are examined. Diffuse and localized (urban) concentrations of CO as pollutant are studied, and anthropogenic sources and sinks for CH4 and CO are considered. Perturbation of the CH4-CO-CO2 cycle, crucial to self-cleansing mechanisms of the troposphere, by anthropogenic CO emissions, and the effect of CO long life as global pollutant, are investigated.

Wofsy, S. C.↗
NASA NTRS1977

A measurement system for the atmospheric trace gases CH4 and CO

A system for measuring ambient clean air levels of the atmospheric trace gases methane and carbon monoxide is described. The analytical method consists of a gas chromatographic technique that incorporates sample preconcentration with catalytic conversion of CO to CH4 and subsequent flame ionization detection of these gases. The system has sufficient sensitivity and repeatability to make the precise measurements required to establish concentration profiles for CO and CH4 in the planetary boundary layer. A discussion of the bottle sampling program being conducted to obtain the samples for the concentration profiles is also presented.

Condon, E. P.↗
NASA NTRS1979

Sensitivity of the predicted CO-OH-CH4 perturbation to tropospheric NOx concentrations

Measurements indicate that ambient NOx(NO + NO2) concentrations vary over at least an order of magnitude in the troposphere. Thus it is of interest to study atmospheric chemistry with NOx concentrations covering this range. In this paper we present steady state calculations which show that as NOx concentrations are increased from very low values, the hydroxyl radical concentration increases at first and then decreases. This change of behavior occurs at a concentration of NO2 of about 0.23 ppb in the model. Also, the response of the atmosphere to increased CO fluxes undergoes a qualitative change as a function of the concentration of NOx. At low levels of NOx concentration, an increase in CO fluxes into the atmosphere depletes the OH concentration and increases the concentrations of CH4 and H2, as reported in the literature. However, at high values of NOx concentration, increased CO fluxes give rise to an increase in the OH concentration and, consequently, a decrease in the concentrations of CH4 and H2.

Hameed, S.↗
NASA NTRS1980

A laser flash photolysis-resonance fluorescence kinetics study of the reaction Cl/2P/ + CH4 yields CH3 + HCl

The technique of laser flash photolysis-resonance fluorescence is employed to study the kinetics of the reaction Cl(2P) + CH4 yields CH3 + HCl over the temperature range 221-375 K. At temperatures less than or equal to 241 K the apparent bimolecular rate constant is found to be dependent upon the identity of the chemically inert gases in the reaction mixture. For Cl2/CH4/He reaction mixtures (total pressure = 50 torr) different bimolecular rate constants are measured at low and high methane concentrations. For Cl2/CH4/CCl/He and Cl2/CH4/Ar reaction mixtures, the bimolecular rate constant is independent of methane concentration, being approximately equal to the rate constant measured at low methane concentrations for Cl2/CH4/He mixtures. These rate constants are in good agreement with previous results obtained using the discharge flow-resonance fluorescence and competitive chlorination techniques. At 298 K the measured bimolecular rate constant is independent of the identity of the chemically inert gases in the reaction mixture and in good agreement with all previous investigations. The low-temperature results obtained in this investigation and all previous investigations can be rationalized in terms of a model which assumes that the Cl(2P 1/2) state reacts with CH4 much faster than the Cl(2P 3/2) state. Extrapolation of this model to higher temperatures, however, is not straightforward.

Ravishankara, A. R.↗
NASA NTRS1983

Prebiotic synthesis in atmospheres containing CH4, CO, and CO2. I - Amino acids

The prebiotic synthesis of amino acids, HCN, H2CO, and NH3 using a spark discharge on various simulated primitive earth atmospheres at 25 C is investigated. Various mixtures of CH4, CO, CO2, N2, NH3, H2O, and H2 were utilized in different experiments. The yields of amino acids (1.2-4.7 percent based on the carbon) are found to be approximately independent of the H2/CH4 ratio and the presence of NH3, and a wide variety of amino acids are obtained. Glycine is found to be almost the only amino acid produced from CO and CO2 model atmospheres, with the maximum yield being about the same for the three carbon sources at high H2/carbon ratios,whereas CH4 is superior at low H2/carbon ratios. In addition, it is found that the directly synthesized NH3 together with the NH3 obtained from the hydrolysis of HCN, nitriles, and urea could have been a major source of ammonia in the atmosphere and oceans of the primitive earth. It is determined that prebiotic syntheses from HCN and H2CO to give products such as purines and sugars and some amino acids could have occurred in primitive atmospheres containing CO and CO2 provided the H2/CO and H2/CO2 ratios were greater than about 1.0.

Schlesinger, G.↗
NASA NTRS1984

Carbon and energy yields in prebiotic syntheses using atmospheres containing CH4, CO and CO2

Yields based on carbon are usually reported in prebiotic experiments, while energy yields (moles/cal) are more useful in estimating the yields of products that would have been obtained from the primitive atmosphere of the earth. Energy yields for the synthesis of HCN and H2CO from a spark discharge were determined for various mixtures of CH4, CO, CO2, H2, H2O, N2 an NH3. The maximum yields of HCN and H2CO from CH4, CO, and CO2 as carbon sources are about 4 x 10 to the -8th moles/cal.

Miller, S. L.↗
NASA NTRS1984

The composition of Saturn's atmosphere at northern temperate latitudes from Voyager IRIS spectra - NH3, PH3, C2H2, C2H6, CH3D, CH4, and the Saturnian D/H isotopic ratio

The vertical distributions and mixing ratios of minor constituents in the northern hemisphere of Saturn are investigated. Results are obtained for NH3, PH3, C2H2, C2H6, CH3D, and CH4; the D/H ratio is obtained from the CH4 and CH3D abundances. The NH3 mixing ratio in the upper atmosphere is found to be compatible with the saturated partial pressure. The inferred PH3/H2 ratio of 1.4 + or - 0.8 x 10 to the -6th is higher than the value derived from the solar P/H ratio. The stratospheric C2H2/H2 and C2H6/H2 ratios are, respectively, 2.1 + or - 1.4 x 10 to the -7th and 3.0 + or - 1.1 x 10 to the -6th; the latter decreases sharply below the 20-50 mbar level. The results for CH3D/H2 and CH4/H2 imply an enrichment of Saturn's upper atmosphere in carbon by a factor of at least three over the solar abundance. The interpretation of two NH3 lines in the five-micron window suggests a NH3/H2 ratio at the two bar level below the solar value.

Courtin, R.↗