Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “radically”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,117 records · Page 62
All sourcesNASA NTRSDOE OSTI
NASA NTRS1988

Detailed mechanism of toluene oxidation and comparison with benzene

A detailed mechanism for the oxidation of toluene in both argon and nitrogen dilutents is presented. The mechanism was used to compute experimentally ignition delay times for shock-heated toluene-oxygen-argon mixtures with resonably good success over a wide range of initial temperatures and pressures. Attempts to compute experimentally measured concentration profiles for toluene oxidation in a turbulent reactor were partially successful. An extensive sensitivity analysis was performed to determine the reactions which control the ignition process and the rates of formation and destruction of various species. The most important step was found to be the reaction of toluene with molecular oxygen, followed by the reactions of hydroperoxyl and atomic oxygen with benzyl radicals. These findings contrast with the benzene oxidation, where the benzene-molecular oxygen reaction is quite unimportant and the reaction of phenyl with molecular oxygen dominates. In the toluene mechanism the corresponding reaction of benzyl radicals with oxygen is unimportant. Two reactions which are important in the oxidation of benzene also influence the oxidation of toluene for several conditions. These are the oxidations of phenyl and cyclopentadienyl radicals by molecular oxygen. The mechanism presented successfully computes the decrease of toluene concentration with time in the nitrogen diluted turbulent reactor. This fact, in addition to the good prediction of ignition delay times, shows that this mechanism can be used for modeling the ignition and combustion process in practical, well-mixed combustion systems.

Bittker, David A.↗
NASA NTRS1988

Modified reaction mechanism of aerated n-dodecane liquid flowing over heated metal tubes

The degradation mechanism of the n-dodecane was studied using a modified jet fuel thermal oxidation tester containing a sample withdrawal system as a reaction vessel. The reaction products were identified using gas chromatography and mass spectorometry. The soluble products were found to consist mainly of C5-C10 n-alkanes and 1-alkenes, C7-C10 aldehydes, tetrahydrofuran derivatives, dodecanol and dodecanone isomers, dodecyl hydroperoxide (ROOH) decomposition products, and C24 alkane isomers. The data from the experiments agreed with those of Hazlett et al. (1977). It was found that alkyl peroxide radical reactions dominate in the autooxidation temperature regime (at T not above 300 C); the dominant path is for the alkyl peroxyl radical to react bimolecularly with fuel to yield primarily alkyl hydroperoxides. The alkyl peroxide radical also undergoes self-termination and unimolecular isomerization and decomposition reactions, to yield smaller amounts of C12 alcohol plus ketone products and tetrahydrofuran derivatives, respectively.

Reddy, K. T.↗
NASA NTRS1989

Laser/Plasma/Chemical-Vapor Deposition Of Diamond

Proposed process for deposition of diamond films includes combination of plasma induced in hydrocarbon feed gas by microwave radiation and irradiation of plasma and substrate by lasers. Deposition of graphite suppressed. Reaction chamber irradiated at wavelength favoring polymerization of CH2 radical into powders filtered out of gas. CH3 radicals, having desired sp3 configuration, remains in gas to serve as precursors for deposition. Feed gas selected to favor formation of CH3 radicals; candidates include CH4, C2H4, C2H2, and C2H6. Plasma produced by applying sufficient power at frequency of 2.45 GHz and adjusting density of gas to obtain electron kinetic energies around 100 eV in low-pressure, low-temperature regime.

Hsu, George C.↗
NASA NTRS1988

Mass spectrometric studies of trimethylindium pyrolysis

The kinetics of the pyrolysis of trimethylindium (TMIn) in He, D2, and H2 carriers was investigated using the atmospheric pressure flow-tube apparatus described by Larsen et al. (1987) and a time-of-flight mass spectrometer. The rate constant for the pyrolysis of TMIn in He was found to be comparable to that found by Jacko and Price (1964) for TMIn in toluene carrier (a radical scavenger), indicating that TMIn decomposes in He not by radical attack of methyl groups, but by homolytic fission. The decomposition of TMIn is enhanced in D2 and H2 carriers, where the principal products are CH3D and C2H6, and CH4 and C2H6, respectively, indicating that the reaction pathway in these carriers is different from those in He and toluene. The pyrolysis in H2 and D2 is attributed to a radical attack by H or D on TMIn. A reaction mechanism involving a short-lived hypervalent DTMIn species was proposed and was tested using numerical modeling techniques.

Buchan, N. I.↗
NASA NTRS1989

Electron Spin Resonance (ESR) studies of returned comet nucleus samples

The most important objective of the Comet Nucleus Sample Returm Mission is to return samples which could reflect formation conditions and evolutionary processes in the early solar nebula. It is expected that the returned samples will consist of fine-grained silicate materials mixed with ices composed of simple molecules such as H2O, NH3, CH4 as well as organics and/or more complex compounds. Because of the exposure to ionizing radiation from cosmic-ray, gamma-ray, and solar wind protons at low temperature, free radicals are expected to be formed and trapped in the solid ice matrices. The kind of trapped radical species together with their concentration and thermal stability can be used as a dosimeter as well as a geothermometer to determine thermal and radiation histories as well as outgassing and other possible alternation effects since the nucleus material was formed. Since free radicals that are known to contain unpaired electrons are all paramagnetic in nature, they can be readily detected and characterized in their native form by the Electron Spin Resonance (ESR) method. In fact, ESR has been shown to be a non-destructive, highly sensitive tool for the detection and characterization of paramagnetic, ferromagnetic, and radiation damage centers in terrestrial and extraterrestrial geological samples. The potential use of ESR as an effective method in the study of returned comet nucleus samples, in particular, in the analysis of fine-grained solid state icy samples is discussed.

Tsay, Fun-Dow↗
NASA NTRS1989

Mechanism of electrical conductivity in an irradiated polyimide

A polyimide was exposed to 1.0 MeV electron radiation. The radiation-induced radical density and dc conductivity were measured at various post-irradiation times. The radiation-induced radical density was found to be correlated to the increased dc conductivity through a hopping model of conductivity. The post-irradiation radical species were identified.

Ries, H. R.↗
NASA NTRS1991

Laboratory simulation of the surface of Halley's Comet

In the past year we have developed a model for the dissociation of icy grains in comets. In general, this model does not predict the radical yield that is observed in the jets of comets. To reproduce these yields, the concentration of the radical's precursors will have to be too high to be consistent with the abundance that we expect in comets. We have also constructed a theoretical model for the formation of ions on icy cometary grains. That model shows that only a small number of the cometary ions could be produced as ions in icy grains if the particle has only positively charged ions. If it contains both positive and negative ions then it could have a higher concentration of ions without violating charge neutrality. When such a particle evaporates, it can release ions with both charges into the gas phase. These ions could produce radicals via dissociative recombination with electrons if they are positive ions or by photoattachment of electrons if they are negative electrons. Finally, an avalanche process involving the acceleration of electrons towards charged particles is evaluated. It is shown that this will not lead directly to gas phase ions, but it might lead to additional ionization and dissociation on the grain.

Jackson, William M.↗
NASA NTRS1990

Evaluated rate constants for selected HCFC's and HFC's with OH and O((sup)1D)

The chemistry of HCFC's and HFC's in the troposphere is controlled by reactions with OH in which a hydrogen atom is abstracted from the halocarbon to form water and a halo-alkyl radical. The halo-alkyl radical subsequently reacts with molecular oxygen to form a peroxy radical. The reactions of HCFC's and HFC's with O(exp1D) atoms are unimportant in the troposphere, but may be important in producing active chlorine of OH in the stratosphere. Here, the rate constants for the reactions of OH and O(exp1D) with many HFC's and HCFC's are evaluated. Recommendations are given for the five HCFC's and three HFC's specified by AFEAS as primary alternatives as well as for all other isomers of C1 and C2 HCFC's and HFC's where rate data exist. In addition, recommendations are included for CH3CCl3, CH2Cl2, and CH4.

Hampson, Robert F.↗
NASA NTRS1990

Atmospheric degradation mechanisms of hydrogen containing chlorofluorocarbons (HCFC) and fluorocarbons (HFC)

The current knowledge of atmospheric degradation of hydrogen containing chlorofluorocarbons (HCFC 22 (CHClF2), HCFC 123 (CHCl2CF3), HCFC 124 (CHClFCF3), HCFC 141b (CFCl2CH3), HCFC 142b (CF2ClCH3)) and fluorocarbons (HFC 125 (CHF2CF3), HFC 134a (CH2FCF3), HFC 152a (CHF2CH3)) is assessed. Except for the initiation reaction by OH radicals, there are virtually no experimental data available concerning the subsequent oxidative breakdown of these molecules. However, from an analogy to the degradation mechanisms of simple alkanes, some useful guidelines as to the expected intermediates and final products can be derived. A noteable exception from this analogy, however, appears for the oxi-radicals. Here, halogen substitution induces new reaction types (C-Cl and C-C bond ruptures) which are unknown to the unsubstituted analogues and which modify the nature of the expected carbonyl products. Based on an evaluation of these processes using estimated bond strength data, the following simplified rules with regards to the chlorine content of the HCFC's may be deduced: (1) HCFC's containing one chlorine atom such as 22 and 142b seem to release their chlorine content essentially instantaneous with the initial attack on the parent by OH radicals, and for HCFC 124, such release is apparently prevented; (2) HCFC's such as 123 and 141b with two chlorine atoms are expected to release only one of these instantaneously; and the second chlorine atom may be stored in potentially long-lived carbonyl compounds such as CF3CClO or CClFO.

Zellner, Reinhard↗
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 NTRS1993

The millimeter-wave spectrum of CaH (X 2Sigma(+))

The millimeter-wave spectrum of the CaH and CaD radicals (X 2Sigma(+)) has been observed in the laboratory via direct absorption spectroscopy. The species were generated by the reaction of calcium vapor, produced in a Broida-type oven, with hydrogen atoms created in a microwave discharge. The six hyperfine components of the N = 0 yields 1 rotational transition of CaH near 254 GHz were resolved and their frequencies determined to an accuracy of +/- 100 kHz. The main hyperfine lines originating in the N = 0 yields 1, 1 yields 2, and 2 yields 3 rotational transitions of CaD were also detected. Spectroscopic constants were determined for both radicals from a nonlinear least squares fit to the data, using a 2Sigma Hamiltonian. These measurements constitute the first laboratory observation of CaH at high spectral resolution, and are essential to the detection of this radical in interstellar space.

Barclay, W. L., Jr.↗
NASA NTRS1993

Laboratory studies of low temperature rate coefficients: The atmospheric chemistry of the outer planets

The objectives are to measure laboratory rate coefficients for key reactions of hydrocarbon molecules and radicals at low temperatures, which are relevant to the atmospheric photochemistry of Saturn, Jupiter, and Titan. Upcoming NASA planetary missions, such as Cassini, will probe the atmosphere of Titan in more detail, offering an excellent opportunity to test kinetic models and to establish fiducial standards for using kinetic models to interpret various parameters of the outer planets. Accurate low temperature kinetic data, which are presently lacking, may require crucial revisions to the rates of formation and destruction and are of utmost importance to the success of these efforts. In this program, several key reactions of ethynyl radicals (C2H) with acetylene (C2H2), methane (CH4), and oxygen (O2), down to temperatures of 170 K were successfully investigated. The experimental apparatus developed in our laboratory for measuring reaction kinetics at low temperatures consists of a laser photolysis/infrared probe laser setup. The rate measurements are carried out as a function of (low) temperature with a transverse flow cell designed specifically for these studies. A 193 nm argon fluoride pulsed excimer laser is used to photolyze a suitable precursor molecule, such as acetylene to produce C2H, and a high resolution, tunable infrared F-center laser (2.3-3.35 mu m) probes the transient concentrations of the radical species directly in absorption to extract the kinetic rate coefficients.

Leone, Stephen R.↗
NASA NTRS1992

Measuring electrically charged particle fluxes in space using a fiber optic loop sensor

The purpose of this program was to demonstrate the potential of a fiber optic loop sensor for the measurement of electrically charged particle fluxes in space. The key elements of the sensor are a multiple turn loop of low birefringence, single mode fiber, with a laser diode light source, and a low noise optical receiver. The optical receiver is designed to be shot noise limited, with this being the limiting sensitivity factor for the sensor. The sensing element is the fiber optic loop. Under a magnetic field from an electric current flowing along the axis of the loop, there is a non-vanishing line integral along the fiber optic loop. This causes a net birefringence producing two states of polarization whose phase difference is correlated to magnetic field strength and thus, current in the optical receiver electronic processing. The objectives in this program were to develop a prototype laser diode powered fiber optic sensor. The performance specification of a minimum detectable current density of 1 (mu)amp/sq m-(radical)Hz, should be at the shot noise limit of the detection electronics. OPTRA has successfully built and tested a 3.2 m diameter loop with 137 turns of low birefringence optical fiber and achieved a minimum detectable current density of 5.4 x 10(exp-5) amps/(radical)Hz. If laboratory space considerations were not an issue, with the length of optical fiber available to us, we would have achieved a minimum detectable current density of 4 x 10(exp -7) amps/(radical)Hz.

Source record↗
NASA NTRS1994

Measurement of atmospheric OH by titration of near-IR fluorescent dyes

Recent research has shown that certain polymethine dyes can be detected at ultratrace levels (greater than or equal to 6x10(exp -14) M) in solution by fluorimetry. These detection limits are possible because of the inherent sensitivity of fluorescence techniques, because the dyes fluoresce in the near infrared region where background interference is negligible, and because powerful infrared diode lasers are now available to improve the signal to noise ratio. Other work has shown that the hydroxyl radical destroys the ability of polymethine dyes to fluoresce. These observations form the basis for a new hydroxyl radical detector that is essentially a fluorometric titrator. Theoretically, the detector should show an acceptable sensitivity and response time. Assuming that the atmospheric HO concentration is about 10(exp -11) moles m(exp -3) (i.e. 10(exp 6) molecules cm(exp -3)), then 10 L of air 'titrated' with 20 mL of 10(exp -11) M dye solution (an easily detected concentration) should result in a drop in the fluorescent signal of 50 percent - a readily detectable change. At a flow rate of 3 L min(exp -1) the sampling time would be 3 minutes. The biggest potential problem is selectivity: other oxidants may also cause the fluorescence signal to be lost. The chemistry of polymethine dyes has not been studied in detail and so no quantitative data are available. However, a survey of the literature suggests that in general HO should react up to six orders of magnitude faster than HO2 and other radicals such as RO2 and RO. It should also react much more rapidly than H2O2 and O3. Thus it may be possible to discriminate kinetically against potential interfering substances. It was shown in the laboratory that 10(exp -4) M H2O2 has little effect on the absorption spectrum of the dye IR125 over a period of hours but that the band at 780 nm is slowly lost in water over a period of days even under argon in the dark. By contrast, DMSO solutions of IR125 are stable.

Betterton, Eric A.↗
NASA NTRS1994

An improved method of measuring tropospheric NO2, NO3, HO2, and RO2 by Matrix Isolation and Electronic Spin Resonance (MIESR)

The MIESR method consists of two steps (1) collection of the radicals present in the ambient air at 77K in a polycrystalline D2O matrix and (2) identification and quantification of the different radicals in the laboratory by Electron Spin Resonance spectroscopy. In step (1), the sampling efficiency for sampling NO2 and RO2 was determined to be greater than or equal to 95 percent, with a measured accuracy of plus or minus 5 percent. In step (2), after collection, the samples are maintained at 77 K and spectra are recorded in the laboratory using a standard 9.5 GHz ESR system (Varian E-line). About 50 individual scans of each spectrum are recorded and digitally averaged in order to improve the signal-to-noise ratio. The ESR-spectra are analyzed with a recently developed numerical procedure which was demonstrated to allow speciation of NO2, NO3, HO2, CH3C(O)O2, and the sum of the alkylperoxy radicals. The detection limit is 5ppt for HO2, RO2, and NO2 and 3ppt for NO3 due to its narrower ESR-linewidth.

Source record↗
NASA NTRS1994

Laboratory studies of chemical and photochemical processes relevant to stratospheric ozone

The purpose of this project is to reduce the uncertainty in several key gas-phase kinetic processes which impact our understanding of stratospheric ozone. The main emphasis of this work is on measuring rate coefficients and product channels for reactions of HO(sub x) and NO(sub x) species in the temperature range 200 K to 240 K relevant to the lower stratosphere. Other areas of study have included infrared spectroscopic studies of the HO2 radical, measurements of OH radical reactions with alternative fluorocarbons, and determination of the vapor pressures of nitric acid hydrates under stratospheric conditions. The results of these studies will improve models of stratospheric ozone chemistry and predictions of perturbations due to human influences. In this annual report, we focus on our recent accomplishments in the quantitative spectroscopy of the HO2 radical. This report details the measurements of the broadening coefficients for the v(sub 2) vibrational band. Further measurements of the vapor pressures of nitric acid hydrates relevant to the polar stratospheric cloud formation indicate the importance of metastable crystalline phases of H2SO4, HNO3, and H2O. Large particles produced from these metastable phases may provide a removal mechanism for HNO3 in the polar stratosphere.

Zahniser, Mark S.↗
NASA NTRS1994

Laboratory kinetic studies of OH and CO2 relevant to upper atmospheric radiation balance

During the first year of this program, we have made considerable progress toward the measurement of the dipole moments of vibrationally excited OH radicals. Our primary accomplishments have been 1) the modification of the original slit jet spectrometer for the study of radical species and 2) the observation of infrared chemiluminescence from the vibrationally excited OH radicals formed in the H + ozone reaction in the supersonic jet. We are optimistic that we will soon observe OH* laser induced fluorescence in the jet. Modulation of this fluorescence with microwave radiation in an applied electric field will be the final step required for the precise determination of the vibrational dependence of the OH dipole moment.

Nelson, David D.↗
NASA NTRS1995

Organic molecules in the gas phase of dense interstellar clouds

Since a previous Committee on Space Research (COSPAR) review on this subject, the number of molecular species identified by astronomers in dense interstellar clouds or in the envelopes expelled by evolved stars has grown from about eighty to approximately one hundred. Recent detections in stellar envelopes include the radical CP, the second phosphorus-containing astronomical molecule; SiN, the first astronomical molecule with a Si-N bond; and the HCCN radical. In the dense interstellar clouds recent detections or verifications of previous possible identifications include the H3O(+) ion, which is a critical intermediary in the production of H2O and O2; the CCO radical, which is isoelectronic with HCCN; the SO(+) ion, which appears to be diagnostic of shock chemistry; two new isomers of cyanoacetylene, HCCNC and CCCNH; and the two cumulenes H2C3 and H2C4. Some recent work is also described on the mapping of interstellar clouds in multiple molecular transitions in order to separate variations in chemical abundance from gradients in physical parameters.

Irvine, W. M.↗