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At least 19 records

Quantum chemical study of methane oxidation species

Work completed on the 2A1 excited state and low-lying dissociative states of the methoxy radical is reported. A manuscript was prepared that reports the characterization of the 2A1 electronic state, the excitation energies and Franck-Condon factors for the 2A1 - 2E system, and the energies of intersection between the 2A1 state and the nearby dissociative states. The minimum excitation energy needed for predissociation of methoxy is predicted along with the corresponding implications for atmospheric chemistry.

Jackels, C. F.

Kinetics of oxygen atom formation during the oxidation of methane behind shock waves

An experimental and analytical study of the formation of oxygen atoms during the oxidation of methane and methane-hydrogen mixtures behind incident shock waves was carried out over the temperature range 1790-2584 K at reaction pressures between 1.2 and 1.7 atm. Oxygen atom levels were determined indirectly by measurement of emission from reaction of O with CO. On the basis of these data and ignition-delay data reported in the literature, a kinetic scheme for methane oxidation was assembled. The proposed kinetic mechanism, in general, predicts higher peak oxygen atom levels than the current oxidation mechanisms proposed by Bowman and Seery and by Skinner and his co-workers.

Jachimowski, C. J.

Further developments in oxidation of methane traces with radiofrequency discharge

The radiofrequency discharge, previously shown to oxidize trace levels of methane in oxygen, was studied with contaminated air at 50, 600, and 760 torr. As with oxygen, the concentration of methane traces could be reduced by several orders of magnitude, and no organic reaction products were detected in the effluent; however, substantial concentrations of NOx (0.1-6%) were formed during treatment. The concentration of NOx was decreased by using a large diameter electrode. There is evidence that the process will oxidize N2 and NO as well as organic impurities in oxygen or oxygen/inert gas atmospheres.

Flamm, D. L.

Stratospheric eddy diffusion coefficients from tracer data

Global distributions of nitrous oxide, methane, ozone, and carbon 14 are used to estimate four sets of stratospheric eddy diffusion coefficients. A photochemical equilibrium model calculates O(3P), O(1D), H, HO2, OH, H2O2, NO, and NO2 densities, as a function of altitude, latitude, and time. The calculated O(1D), OH, and observed Cl densities are used to obtain the eddy profiles associated with the methane and nitrous oxide distributions, for altitudes between 10 and 40 km. Application of a constant flux condition to the seasonally averaged ozone data yields eddy values below 20 km. Time-dependent carbon 14 calculations produce eddy coefficients between 13 and 27 km. A composite profile is obtained by comparing the four sets of coefficients. Further, carbon 14 computations are used to test these profiles as well as those recommended in reports issued by the National Academy of Sciences in 1976 and 1979. The composite eddy profile produces the best agreement.

Massie, S. T.

Summary of aircraft results for 1978 southeastern Virginia urban plume measurement study of ozone, nitrogen oxides, and methane

Ozone production was determined from aircraft and surface in situ measurements, as well as from an airborne laser absorption spectrometer. Three aircraft and approximately 10 surface stations provided air-quality data. Extensive meteorological, mixing-layer-height, and ozone-precursor data were also measured. Approximately 50 hrs (9 flight days) of data from the aircraft equipped to monitor ozone, nitrogen oxides, dewpoint temperature, and temperature are presented. In addition, each experiment conducted is discussed.

Gregory, G. L.

A photochemical theory of tropospheric ozone

We present a photochemical theory for tropospheric ozone in which the methane oxidation chain constitutes a large local source. This source produces about one trillion odd oxygen molecules per square centimeter per second and implies a photochemical lifetime for ozone of about 1 day, much shorter than characteristic mixing times. The photochemical model reproduces the altitude and seasonal dependence of ozone at 30 deg N. It also gives qualitative agreement with observed day-to-day variations of the ozone density.

Chameides, W.

Greenhouse effects due to man-made perturbations of trace gases

Nitrous oxide, methane, ammonia, and a number of other trace constituents of the earth's atmosphere have infrared absorption bands in the spectral range from 7 to 14 microns. Despite their small amounts, these gases can have a significant effect on the thermal structure of the atmosphere by transmitting most of the thermal radiation from the earth's surface to the lower atmosphere. In the present paper, this greenhouse effect is computed for a number of trace gases. The nature and climatic implications of possible changes in the concentrations of N2O, CH4, NH3, and HNO3 are discussed.

Wang, W. C.

Distribution, abundance and carbon isotopic composition of gaseous hydrocarbons in Big Soda Lake, Nevada - An alkaline, meromictic lake

The study of the distribution and isotopic composition of low molecular weight hydrocarbon gases at the Big Soda Lake, Nevada, has shown that while neither ethylene nor propylene were found in the lake, ethane, propane, isobutane and n-butane concentrations all increased with water column depth. It is concluded that methane has a biogenic origin in both the sediments and the anoxic water column, and that C2-C4 alkanes have biogenic origins in the monimolimnion water and shallow sediments. The changes observed in delta C-13/CH4/ and CH4/(C2H6 + C3H8) with depth in the water column and sedimeents are probably due to bacterial processes, which may include anaerobic methane oxidation and different rates of methanogenesis, and C2-to-C4 alkane production by microorganisms.

Oremland, R. S.

Oxidation of contaminative methane traces with radio-frequency discharge

An 11.8 MHz glow discharge was used to oxidize trace levels of methane in oxygen. The concentration of methane can be reduced by three orders of magnitude. The effects of power (0-400 W), flow rate (10-1000 cc-STP/min) and concentration (70-8000 ppm) were investigated at pressures ranging from 50 torr to almost 1 atm. No organic reaction products were detected in the treated gas stream. The process may prove useful for the removal of atmospheric trace contaminants at ambient pressure.

Flamm, D. L.

Reactions of O/1D/ with methane and ethane.

Mixtures of nitrous oxide and methane and mixtures of nitrous oxide and ethane were photolyzed with 1849-A light. The reaction products were analyzed chromatographically. It was found that the reaction of the excited atomic oxygen with methane gives mainly CH3 and OH radicals as initial products, along with about 9% of formaldehyde and molecular hydrogen. The reaction of the excited atomic oxygen with ethane gives C2H5, OH, CH3 and CH2OH as major initial products, with only a few per cent of molecular hydrogen.

Lin, C.-L.

Analytical study of mechanisms for nitric oxide formation during combustion of methane in a jet-stirred combustor

The role of chemical kinetics in the formation of nitric oxide during the combustion of methane was examined analytically by means of a detailed chemical mechanism for the oxidation of methane, for the reaction between hydrocarbon fragments, and for the formation of nitric oxide. By comparing predicted nitric oxide levels with values reported in the literature from jet-stirred combuster experiments, it was determined that the nitric oxide levels observed in fuel-rich flames cannot be described by a mechanism in which the rate of nitric oxide formation is controlled solely by the kinetics of oxygen atom formation. A proposed mechanism for the formation of nitric oxide in methane-rich flames reproduces the observed levels. The oxidation of hydrogen cyanide appears to be an important factor in nitric oxide formation.

Jachimowski, C. J.

Catalytic oxidation of trace levels of methane in oxygen in a tubular reactor

An experimental investigation of catalytic oxidation of trace levels of methane in oxygen was conducted in a tubular reactor. Two noble metal solid catalysts were explored: a 1-percent platinum on gamma alumina and a 0.5-percent rhodium on gamma alumina. For each catalyst the activity was determined as a function of temperature, pressure, space velocity, and methane concentration. The rhodium catalyst was considerably more active than the platinum catalyst. For each catalyst mass transfer had a pronounced effect upon activity at low space velocity.

Warshay, M.

Production of nitrous oxide and consumption of methane by forest soils

Soils in an Amazonian rainforest are observed to release N2O at a rate larger than the global mean by about a factor of 20. Emissions from a New England hardwood forest are approximately 30 times smaller then Brazilian values. Atmospheric methane is consumed by soils in both systems. Tropical forests would provide a major source of atmospheric N2O if the Brazilian results are representative.

Keller, M.