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At least 109 records · Page 6

New method for determining heats of combustion of gaseous hydrocarbons

As a spin off of a system developed for monitoring and controlling the oxygen concentration in the Langley 8-foot High Temperature Tunnel, a highly accurate on-line technique was developed for determining heats of combustion of natural gas samples. It is based on measuring the ratio m/n, where m is the (volumetric) flowrate of oxygen required to enrich the carrier air in which the test gas flowing at the rate n is burned, such that the mole fraction of oxygen in the combustion product gases equals that in the carrier air. The m/n ratio is directly related to the heats of combustion of the saturated hydrocarbons present in the natural gas. A measurement of the m/n ratio for the test gas can provide a direct means of determination of its heat of combustion by using the calibration graph relating the m/n values for pure saturated hydrocarbons with their heats of combustion. The accuracy of the technique is determine solely by the accuracy with which the flowrates m and n can be measured and is of the order of 2 percent in the present study. The theoretical principles and experimental results are discussed.

Singh, J. J.↗

Determination of solid mass fraction in partially frozen hydrocarbon fuels

Filtration procedures alone are insufficient to determine the amounts of crystalline solid in a partially frozen hydrocarbon distillate fraction. This is due to the nature of the solidification process by which a large amount of liquid becomes entrapped within an interconnected crystalline structure. A technique has been developed to supplement filtration methods with an independent determination of the amount of liquid in the precipitate thereby revealing the actual value of mass percent crystalline solid, %S. A non-crystallizing dye is injected into the fuel and used as a tracer during the filtration. The relative concentrations of the dye in the filtrate and precipitate fractions is subsequently detected by a spectrophotometric comparison. The filtration apparatus was assembled so that the temperature of the sample is recorded immediately above the filter. Also, a second method of calculation has been established which allows significant reduction in test time while retaining acceptable accuracy of results. Data have been obtained for eight different kerosene range hydrocarbon fuels.

Cotterell, E. M.↗

Shock-tube pyrolysis of chlorinated hydrocarbons - Formation of soot

Soot formation in pyrolysis of chlorinated methanes, their mixtures with methane, and chlorinated ethylenes were studied behind reflected shock waves by monitoring the attenuation of an He-Ne laser beam. An additional single-pulse shock-tube study was conducted for the pyrolysis of methane, methyl chloride, and dichloromethane. The experiments were performed at temperatures 1300-3000 K, pressures of 0.4-3.6 bar, and total carbon atom concentrations of 1-5 x 10 to the 17th atoms cu cm. The amounts of soot produced in the pyrolysis of chlorinated hydrocarbons are larger than that of their nonchlorinated counterparts. The sooting behavior and product distribution can be generally explained in terms of chlorine-catalyzed chemical reaction mechanisms. The pathway to soot from chlorinated methanes and ethylenes with high H:Cl ratio proceeds via the formation of C2H, C2H2, and C2H3 species. For chlorinated hydrocarbons with low H:Cl ratio, the formation of C2 and its contribution to soot formation at high temperatures becomes significant. There is evidence for the importance of CHCl radical and its reactions in the pyrolysis of dichloromethane.

Frenklach, M.↗

The possible existence of interstellar Polycyclic Aromatic Hydrocarbons (PAHs) in collected interplanetary dust particles

Extraterrestrial dust particles which are 3 to 50 microns in size are routinely collected in the stratosphere and are now available for general laboratory study. These grains represent true Interplanetary Dust Particles (IDPs). Issues associated with the carbon containing components of IDPs which occur in a variety of physical forms, including amorphous mantles and matrix materials, are addressed. The observed properties of the hydrocarbon phase in IDPs are compared with those expected for polycyclic aromatic hydrocarbons (PAHs).

Sandford, S. A.↗

Method and device for determining heats of combustion of gaseous hydrocarbons

A method and device is provided for a quick, accurate and on-line determination of heats of combustion of gaseous hydrocarbons. First, the amount of oxygen in the carrier air stream is sensed by an oxygen sensing system. Second, three individual volumetric flow rates of oxygen, carrier stream air, and hydrocrabon test gas are introduced into a burner. The hydrocarbon test gas is fed into the burner at a volumetric flow rate, n, measured by a flowmeter. Third, the amount of oxygen in the resulting combustion products is sensed by an oxygen sensing system. Fourth, the volumetric flow rate of oxygen is adjusted until the amount of oxygen in the combustion product equals the amount of oxygen previously sensed in the carrier air stream. This equalizing volumetric flow rate is m and is measured by a flowmeter. The heat of combustion of the hydrocrabon test gas is then determined from the ratio m/n.

Singh, Jag J.↗

Solid hydrocarbon aerosols produced in simulated Uranian and Neptunian stratospheres

Solid hydrocarbon films were deposited in an RF plasma discharge of various CH4/H2/He mixtures under conditions simulating the formation of solid aerosols by magnetospheric charged particles in the stratospheres of Uranus and Neptune. The percentage of CH4 ranged from 0.0002 to 100 percent; the pressure in the discharge chamber was either 130 or 660 microbar; and the films produced were yellow to deep red-brown in color and 2-25 microns thick. The real and imaginary parts of the refractive index at wavelengths from 350 nm to 2.5 microns were determined for all the films, and the results are compared with observational data and the predictions of theoretical models in extensive tables and graphs. Good agreement is demonstrated, suggesting that aerosol production by this mechanism may be competitive with UV or charged-particle irradiation of hydrocarbon condensates.

Khare, B. N.↗

Light hydrocarbons from plasma discharge in H2-He-CH4 - First results and Uranian auroral chemistry

The production of light hydrocarbons by precipitating magnetospheric electrons in the Uranian stratosphere is simulated in laboratory experiments. The products of continuous-flow glow discharges of H2-He-CH4 mixtures containing 0.0012 or 0.022 mol pct CH4 at pressures 0.63-57 mbar are trapped at 77 K, measured manometrically, and identified by gas chromatography and mass spectroscopy; the results are presented in tables and characterized in detail. The globally averaged rate for the production of higher hydrocarbons by this mechanism on Uranus is estimated as 3 x 10 to the 6th C/sq cm sec and shown to be similar to that for photochemical production, while the local rate for the auroral zones is significantly higher than the corresponding photochemical rate. A decrease in yield with increasing molecular complexity is also noted.

Thompson, W. Reid↗

Measurements of atmospheric hydrocarbons and biogenic emission fluxes in the Amazon boundary layer

Tropospheric mixing ratios of methane, C2-C10 hydrocarbons, and carbon monoxide were measured over the Amazon tropical forest near Manaus, Amazonas, Brazil, in July and August 1985. The measurements, consisting mostly of altitude profiles of these gases, were all made within the atmospheric boundary layer up to an altitude of 1000 m above ground level. Data characterize the diurnal hydrocarbon composition of the boundary layer. Biogenic emissions of isoprene control hydroxyl radical concentrations over the forest. Biogenic emission fluxes of isoprene and terpenes are estimated to be 25,000 micrograms/sq m per day and 5600 micrograms/sq m per day, respectively. This isoprene emission is equivalent to 2 percent of the net primary productivity of the tropical forest. Atmospheric oxidation of biogenic isoprene and terpenes emissions from the Amazon forest may account for daily increases of 8-13 ppb for carbon monoxide in the planetary boundary layer.

Zimmerman, P. R.↗

Liquid Oxygen Cooling of Hydrocarbon Fueled Rocket Thrust Chambers

Rocket engines using liquid oxygen (LOX) and hydrocarbon fuel as the propellants are being given serious consideration for future launch vehicle propulsion. Normally, the fuel is used to regeneratively cool the combustion chamber. However, hydrocarbons such as RP-1 are limited in their cooling capability. Another possibility for the coolant is the liquid oxygen. Combustion chambers previously tested with LOX and RP-1 as propellants and LOX as the collant demonstrated the feasibility of using liquid oxygen as a coolant up to a chamber pressure of 13.8 MPa (2000 psia). However, there was concern as to the effect on the integrity of the chamber liner if oxygen leaks into the combustion zone through fatigue cracks that may develop between the cooling passages and the hot gas side wall. In order to study this effect, chambers were fabricated with slots machined upstream of the throat between the cooling passage wall and the hot gas side wall to simulate cracks. The chambers were tested at a nominal chamber pressure of 8.6 MPa (1247 psia) over a range of mixture ratios from 1.9 to 3.1 using liquid oxygen as the coolant. The results of the testing showed that the leaking LOX did not have a deleterious effect on the chambers in the region of the slots. However, there was unexplained melting in the throat region of both chambers, but not in line with the slots.

Armstrong, Elizabeth S.↗

Measurements of selected C2-C5 hydrocarbons in the troposphere - Latitudinal, vertical, and temporal variations

The tropospheric distribution of 1077 C2-C5 hydrocarbon samples was determined. Shipboard measurements obtained over the eastern Pacific Ocean reveal large north-to-south gradients for most nonmethane hydrocarbons (NMHCs). The results show that NMHC concentrations can decrease by a factor of two or more during the passage of cold fronts in winter and spring, and that upper tropospheric concentrations were lower than those in the lower troposphere.

Singh, Hanwant B.↗

Formation of polycyclic aromatic hydrocarbons in circumstellar envelopes

Production of polycyclic aromatic hydrocarbons in carbon-rich circumstellar envelopes was investigated using a kinetic approach. A detailed chemical reaction mechanism of gas-phase PAH formation and growth, containing approximately 100 reactions of 40 species, was numerically solved under the physical conditions expected in cool stellar winds. The chemistry is based on studies of soot production in hydrocarbon pyrolysis and combustion. Several first-ring and second-ring cyclization processes were considered. A linear lumping algorithm was used to describe PAH growth beyond the second aromatic ring. PAH production using this mechanism was examined with respect to a grid of idealized constant velocity stellar winds as well as several published astrophysical models. The basic result is that the onset of PAH production in the interstellar envelopes is predicted to occur within the temperature interval of 1100 to 900 K. The absolute amounts of the PAHs formed, however, are very sensitive to a number of parameters, both chemical and astrophysical, whose values are not accurately known. Astrophysically meaningful quantities of PAHs require particularly dense and slow stellar winds and high initial acetylene abundance. It is suggested that most of the PAHs may be produced in a relatively small fraction of carbon-rich red giants.

Frenklach, Michael↗

Liquid oxygen cooling of hydrocarbon fueled rocket thrust chambers

Rocket engines using liquid oxygen (LOX) and hydrocarbon fuel as the propellants are being given serious consideration for future launch vehicle propulsion. Normally, the fuel is used to regeneratively cool the combustion chamber. However, hydrocarbons such as RP-1 are limited in their cooling capability. Another possibility for the coolant is the liquid oxygen. Combustion chambers previously tested with LOX and RP-1 as propellants and LOX as the coolant demonstrated the feasibility of using liquid oxygen as a coolant up to a chamber pressure of 13.8 MPa (2000 psia). However, there was concern as to the effect on the integrity of the chamber liner if oxygen leaks into the combustion zone through fatigue cracks that may develop between the cooling passages and the hot gas side wall. In order to study this effect, chambers were fabricated with slots machined upstream of the throat between the cooling passage wall and the hot gas side wall to simulate cracks. The chambers were tested at a nominal chamber pressure of 8.6 MPa (1247 psia) over a range of mixture ratios from 1.9 to 3.1 using liquid oxygen as the coolant. The results of the testing showed that the leaking LOX did not have a deleterious effect on the chambers in the region of the slots. However, there was unexplained melting in the throat region of both chambers, but not in line with the slots.

Armstrong, Elizabeth S.↗

Hydrocarbon-fuel/combustion-chamber-liner materials compatibility

Results of material compatibility experiments using hydrocarbon fuels in contact with copper-based combustion chamber liner materials are presented. Mil-Spec RP-1, n- dodecane, propane, and methane fuels were tested in contact with OFHC, NASA-Z, and ZrCu coppers. Two distinct test methods were employed. Static tests, in which copper coupons were exposed to fuel for long durations at constant temperature and pressure, provided compatibility data in a precisely controlled environment. Dynamic tests, using the Aerojet Carbothermal Test Facility, provided fuel and copper compatibility data under realistic booster engine service conditions. Tests were conducted using very pure grades of each fuel and fuels to which a contaminant, e.g., ethylene or methyl mercaptan, was added to define the role played by fuel impurities. Conclusions are reached as to degradation mechanisms and effects, methods for the elimination of these mechanisms, selection of copper alloy combustion chamber liners, and hydrocarbon fuel purchase specifications.

Gage, Mark L.↗

A unifying picture of gas-phase formation and growth of PAH (Polycyclic Aromatic Hydrocarbons), soot, diamond and graphite

A variety of seemingly different carbon formation processes -- polycyclic aromatic hydrocarbons and diamond in the interstellar medium, soot in hydrocarbon flames, graphite and diamond in plasma-assisted-chemical vapor deposition reactors -- may all have closely related underlying chemical reaction mechanisms. Two distinct mechanisms for gas-phase carbon growth are discussed. At high temperatures it proceeds via the formation of carbon clusters. At lower temperatures it follows a polymerization-type kinetic sequence of chemical reactions of acetylene addition to a radical, and reactivation of the resultant species through H-abstraction by a hydrogen atom.

Frenklach, Michael↗

Heavy hydrocarbon main injector technology

One of the key components of the Advanced Launch System (ALS) is a large liquid rocket, booster engine. To keep the overall vehicle size and cost down, this engine will probably use liquid oxygen (LOX) and a heavy hydrocarbon, such as RP-1, as propellants and operate at relatively high chamber pressures to increase overall performance. A technology program (Heavy Hydrocarbon Main Injector Technology) is being studied. The main objective of this effort is to develop a logic plan and supporting experimental data base to reduce the risk of developing a large scale (approximately 750,000 lb thrust), high performance main injector system. The overall approach and program plan, from initial analyses to large scale, two dimensional combustor design and test, and the current status of the program are discussed. Progress includes performance and stability analyses, cold flow tests of injector model, design and fabrication of subscale injectors and calorimeter combustors for performance, heat transfer, and dynamic stability tests, and preparation of hot fire test plans. Related, current, high pressure, LOX/RP-1 injector technology efforts are also briefly discussed.

Fisher, S. C.↗

Stable hydrogen and carbon isotope ratios of extractable hydrocarbons in the Murchison meteorite

A fairly fool-proof method to ensure that the compounds isolated from meteorites are truly part of the meteorites and not an artifact introduced by exposure to the terrestrial environment, storage, or handling is presented. The stable carbon and hydrogen isotope ratios in several of the chemical compounds extracted from the Murchison meteorite were measured. The results obtained by studying the amino acids in this meteorite gave very unusual hydrogen and carbon isotope ratios. The technique was extended to the different classes of hydrocarbons and the hydrocarbons were isolated using a variety of separation techniques. The results and methods used in this investigation are described in this two page paper.

Krishnamurthy, R. V.↗

Aliphatic hydrocarbons of the Murchison meteorite

Hydrocarbon fractions from the Murchison meteorite were prepared using benzene-methanol as the extraction solvent, fractionated on silica gel columns, and analyzed using gas chromatography combined with mass spectrometry and IR and NMR techniques. Results indicate that the most abundant aliphatic hydrocarbon components of the Murchison meteorite are C15 to C30 branched-alkyl-substituted mono-, di-, and tricyclic alkanes. It is shown that the n-alkanes, methyl alkanes, and isoprenoid alkanes that are sometimes found in extracts of the Murchison meteorite are terrestrial contaminants.

Cronin, John R.↗

Natural hydrocarbons, urbanization, and urban ozone

The combined effects of emission control and urbanization, with its concomitant intensification of the urban heat island, on urban ozone concentrations are studied. The effect of temperature on ozone is considered, and attention is given to the temperature effect on ozone photochemistry. Model calculations suggest that ozone concentration enhancements are caused by the effect of temperature on the atmospheric chemistry of peroxyacetyl nitrate, as well as the temperature dependence of natural and anthropogenic hydrocarbon emissions. It is pointed out that, because of the sensitivity of urban ozone to local climatic conditions and the ability of trees to moderate summertime temperatures, the inadvertent removal of trees from urbanization can have an adverse effect on urban ozone concentration, while a temperature increase in the urban heat island caused by urbanization can essentially cancel out the ozone-reducing benefits obtained from a 50-percent reduction in anthropogenic hydrocarbon emissions.

Cardelino, C. A.↗