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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.

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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
NASA NTRS1997

Kinetics and Thermochemistry of the Cl((sup 2)P(sub J)) + C2Cl4 Association Reaction

A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of the Cl(sup 2)P(sub j) + C2Cl4 association reaction as a function of temperature (231-390 K) and pressure (3-700 Torr) in nitrogen buffer gas. The reaction is found to be in the falloff regime between third and second order over the range of conditions investigated, although the second-order limit is approached at the highest pressures and lowest temperatures. At temperatures below 300 K, the association reaction is found to be irreversible on the experimental time scale of approximately 20 m-s. The kinetic data at T is less than 300 K have been employed to obtain falloff parameters in a convenient format for atmospheric modeling. At temperatures above 330 K, reversible addition is observed, thus allowing equilibrium constants for C2Cl5 formation and dissociation to be determined. Second- and third-law analyses of the equilibrium data lead to the following thermochemical parameters for the association reaction: Delta-H(298) = -18.1 +/- 1.3 kcal/mol, Delta-H(0) = -17.6 +/- 1.3 kcal/mol, and Delta-S(298) = -27.7 +/- 3.0 cal/mol.K. In conjunction with the well-known heats of formation of Cl((sup 2)P(sub j)) and C2Cl4 the above Delta-H values lead to the following heats of formation for C2Cl5, at 298 and 0 K: Delta-H(f,298) = 8.0 +/- 1.3 kcal/mol and Delta-H(f,0) = 8.1 +/- 1.5 kcal/mol. The kinetic and thermochemical parameters reported above are compared with other reported values, and the significance of reported association rate coefficients for understanding tropospheric chlorine chemistry is discussed.

Nicovich, J. M.↗
NASA NTRS1976

Absolute rate parameters for the reaction of ground state atomic oxygen with dimethyl sulfide and episulfide

It is pointed out that the investigated reaction of oxygen with dimethyl sulfide may play an important role in photochemical smog formation and in the chemical evolution of dense interstellar clouds. Kinetic data were obtained with the aid of the flash photolysis-resonance fluorescence method. The photodecomposition of molecular oxygen provided the oxygen atoms for the experiments. The decay of atomic oxygen was studied on the basis of resonance fluorescence observations. Both reactions investigated were found to be fast processes. A negative temperature dependence of the rate constants for reactions with dimethyl sulfide was observed.

Lee, J. H.↗
NASA NTRS1977

Product distributions for some thermal energy charge transfer reactions of rare gas ions

Ion cyclotron resonance methods were used to measure the product distributions for thermal-energy charge-transfer reactions of He(+), Ne(+), and Ar(+) ions with N2, O2, CO, NO, CO2, and N2O. Except for the He(+)-N2 reaction, no molecular ions were formed by thermal-energy charge transfer from He(+) and Ne(+) with these target molecules. The propensity for dissociative ionization channels in these highly exothermic charge-transfer reactions at thermal energies contrasts with the propensity for formation of parent molecular ions observed in photoionization experiments and in high-energy charge-transfer processes. This difference is explained in terms of more stringent requirements for energy resonance and favorable Franck-Condon factors at thermal ion velocities.

Anicich, V. G.↗
NASA NTRS1978

A kinetics investigation of several reactions involving chlorine containing compounds

The technique of flash photolysis-resonance fluorescence was utilized to study nine reactions of stratospheric importance. The tropospheric degradation reactions of seven halogenated hydrocarbons were studied to assess their possible influx into the stratosphere. There are reactions of either Cl, OH, or O(3P) species with hydrogenated species, O3 or chlorinated compounds. Apart from the kinetic measurements, the quantum yield for the production of O(1D) from O3 in the crucial wavelength region of 293 to 316.5 nm was studied by utilizing a narrow wavelength laser as the photolysis source. The product formation was monitored by measuring the fluorescence of NO2 formed through O(1D) reaction with N2O followed by NO reaction with O3 to give NO2.

Davis, D. D.↗
NASA NTRSDate not supplied

Surrogate Fuel Chemistry from ReaxFF Molecular Dynamics

Reactive molecular dynamics with ReaxFF simulations are used to study the chemistry of four component jet fuel mixtures of n-dodecane, iso-octane, n-propylbenzene, and mesitylene. ReaxFF does not require knowledge of the chemistry a priori providing insight into reactions otherwise not seen in established chemical kinetic mechanisms. The results show that a difference in the local chemical environment can change the fuel decomposition pathways across the surrogate mixtures where the same fuel species are used. These simulations highlight the need to consider cross-chemical interactions in chemical kinetic mechanism development and the importance of resonance stabilized polyaromatic hydrocarbon reactions for soot growth and formation. A method for predicting the threshold sooting index from the carbon species formed at the end of the simulations is established. The results of the simulations are consistent with measurements of the threshold sooting index with the predicted values within 20% of the measured data

Surrogate Fuels↗
NASA NTRS2008

Synchrotron Photoionization Mass Spectrometry Measurements of Kinetics and Product Formation in the Allyl Radical (H2CCHCH2)Self Reaction

Product channels for the self-reaction of the resonance-stabilized allyl radical, C3H5 + C3H5, have been studied with isomeric specificity at temperatures from 300-600 K and pressures from 1-6 Torr using time-resolved multiplexed photoionization mass spectrometry. Under these conditions 1,5-hexadiene was the only C6H10 product isomer detected. The lack of isomerization of the C6H10 product is in marked contrast to the C6H6 product in the related C3H3 + C3H3 reaction, and is due to the more saturated electronic structure of the C6H10 system. The disproportionation product channel, yielding allene + propene, was also detected, with an upper limit on the branching fraction relative to recombination of 0.03. Analysis of the allyl radical decay at 298 K yielded a total rate coefficient of (2.7 +/- 0.8) x 10(exp -11) cu cm/molecule/s, in good agreement with pre.vious experimental measurements using ultraviolet kinetic absorption spectroscopy and a recent theoretical determination using variable reaction coordinate transition state theory. This result provides independent indirect support for the literature value of the allyl radical ultraviolet absorption cross-section near 223 nm.

Selby, Talitha M.↗
NASA NTRS1978

Reactions of OH/+/ and H2O/+/ ions with some diatomic and simple polyatomic molecules

The rate constants and product distributions of the reactions of OH(+) and H2O(+) with some diatomic and simple polyatomic molecules were studied by ion cyclotron resonance (ICR) mass spectrometric techniques. Reaction rates with CO, NO, O2, N2, CO2, H2S, N2O, H2CO, CH4 and CD4 were measured. Charge transfer and proton transfer were generally observed in cases for which the reaction channel is exothermic, but processes involving rearrangement were not found.

Karpas, Z.↗
NASA NTRS1998

Carbon-13 Labeling Used to Probe Cure and Degradation Reactions of High- Temperature Polymers

High-temperature, crosslinked polyimides are typically insoluble, intractible materials. Consequently, in these systems it has been difficult to follow high-temperature curing or long-term degradation reactions on a molecular level. Selective labeling of the polymers with carbon-13, coupled with solid nuclear magnetic resonance spectrometry (NMR), enables these reactions to be followed. We successfully employed this technique to provide insight into both curing and degradation reactions of PMR-15, a polymer matrix resin used extensively in aircraft engine applications.

Meador, Mary Ann B.↗
NASA NTRS1991

Lifetime measurement of a collision complex using ion cyclotron double resonance - H2C6N2(+)

In the ion-molecule reaction between HC3N(+) and HC3N, the lifetime of the collision complex (H2C6N2+)-asterisk was long enough that ion cyclotron double-resonance techniques could be used to probe the distribution of the lifetimes of the collision complex. The mean lifetime of the collision complex at room temperature was measured as 180 microsec with a distribution ranging from 60 to 260 microsec as measured at the half-heights in the distribution. Lifetimes of this magnitude with respect to unimolecular dissociation allow for some stabilization of the collision complex by the slower process of infrared photon emission.

Anicich, Vincent G.↗
NASA NTRS1979

Resonant charge transfer in He/+/-He collisions studied with the merging-beams technique

Absolute cross sections are reported for the resonant charge-transfer reaction He(+) + He yields He + He(+) at collision energies between 0.1 and 187 eV. The results, obtained using a new merging-beam apparatus are in agreement both with theory and with measurements made using other experimental techniques. The experimentally determined cross sections between 0.5 and 187 eV fall about a line given by sigma exp 1/2(sq-A) = 5.09-2.99 lnW, where W is the collision energy in eV. Considerable attention is paid to the configuration and operation of the apparatus. Tests and calculations which confirm the interpretation of the experimental data in a merging-beam experiment are discussed.

Rundel, R. D.↗
NASA NTRS1990

UV and VUV spectroscopy and photochemistry of small molecules in a supersonic jet

UV and VUV absorption and emission spectroscopy is used to probe jet cooled molecules, free radicals, and clusters in the gas phase. Due to efficient cooling inhomogeneous effects on spectral line widths are eliminated. Therefore from these spectra, both structural and dynamical information is obtained. The photoproducts of these reactions are probed by resonance enhanced multiphoton ionization.

Ruehl, E.↗
NASA NTRS2003

Functional organization of human intraparietal and frontal cortex for attending, looking, and pointing

We studied the functional organization of human posterior parietal and frontal cortex using functional magnetic resonance imaging (fMRI) to map preparatory signals for attending, looking, and pointing to a peripheral visual location. The human frontal eye field and two separate regions in the intraparietal sulcus were similarly recruited in all conditions, suggesting an attentional role that generalizes across response effectors. However, the preparation of a pointing movement selectively activated a different group of regions, suggesting a stronger role in motor planning. These regions were lateralized to the left hemisphere, activated by preparation of movements of either hand, and included the inferior and superior parietal lobule, precuneus, and posterior superior temporal sulcus, plus the dorsal premotor and anterior cingulate cortex anteriorly. Surface-based registration of macaque cortical areas onto the map of fMRI responses suggests a relatively good spatial correspondence between human and macaque parietal areas. In contrast, large interspecies differences were noted in the topography of frontal areas.

NASA Discipline Neuroscience↗
NASA NTRS1984

Kinetics of the reaction Cl + NO2 + M

Using atomic chlorine resonance fluorescence at 140 nm to detect the decay of atomic chlorine in the presence of an excess of NO2, the rate constant for the reaction Cl + NO2 + M, where M is the total gas concentration, is measured over the temperature range 264 to 417 K and at a pressure 1 to 7 torr in a discharge flow system. The rate constants for M= He and M= N2 are measured and the results are summarized in a table. The systematic error of the rate constants is estimated to be about 15 percent. A static photolysis system coupled with an FTIR spectrophotometer is used to determine the branching ratio for the formation of two possible isomers. The ratio is concluded to be ClONO (greater than or equal 75 percent) and ClNO2 (less than or equal 25 percent) which is in agreement with the results of Niki et al. (1978).

Leu, M.-T.↗
NASA NTRS1976

Atom-radical reaction systems

A laminar flow through resonance fluorescence technique, which permits the direct measurement of absolute density for most atomic and diatomic constituents in the stratosphere was developed. This system is shown schematically and its use in determining O(3p) and OH densities is described.

Anderson, J. G.↗
NASA NTRS1990

Association reactions at low pressure. III - The C2H2(+)/C2H2 system

An ion cyclotron resonance mass spectrometer is used to examine the association reactions, C4H2(+) + C2H2 and C4H3(+) + C2H2, at pressures in the range of 8 x 10 to the -8 to 1 x 10 to the -4 Torr at 298 K. The association of C4H2(+) and C4H3(+) with C2H2 was found to exhibit classical behavior in the pressure range of 5 x 10 to the -8 Torr to 0.4 Torr. It is found that an efficient route via radiative association exists for unsaturated hydrocarbon cations to convert to aromatic structures in the presence of acetylene.

Anicich, Vincent G.↗
NASA NTRS1981

An ICR investigation of ion-molecule reactions of HCN

Laboratory reaction rates and product distributions measured by the ion cyclotron resonance technique are reported for a series of reactions of HCN(+) ions with the neutral molecules HCN, CH4, NH3, H2O, CO, CO2, N2 and O2. Rate coefficients are also reported for reactions of positive ions derived from these molecules with HCN. A comparison of the results with a survey of literature values for rate coefficients of HCN(+) reactions shows some exothermic proton transfers from HCN(+) to be inefficient.

Mcewan, M. J.↗
NASA NTRS2003

Studies of Atomic Free Radicals Stored in a Cryogenic Environment

Impurity-Helium Solids are porous gel-like solids consisting of impurity atoms and molecules surrounded by thin layers of solid helium. They provide an ideal medium for matrix isolation of free radicals to prevent recombination and store chemical energy. In this work electron spin resonance, nuclear magnetic resonance, X-ray diffraction, and ultrasound techniques have all been employed to study the properties of these substances. Detailed studies via electron spin resonance of exchange tunneling chemical reactions involving hydrogen and deuterium molecular and atomic impurities in these solids have been performed and compared with theory. Concentrations of hydrogen approaching the quantum solid criterion have been produced. Structured studies involving X ray diffraction, ultrasound, and electron spin resonance have shown that the impurities in impurity helium solids are predominantly contained in impurity clusters, with each cluster being surrounded by thin layers of solid helium.

Lee, David M.↗
NASA NTRS1984

The rate of the reaction of OH with HCl

Using the techniques of laser/flash photolysis-resonance fluorescence, the absolute rate constant for the OH + HCl reaction is measured from 240 to 295 K. Ultraviolet and infrared spectrophotometry are used to continuously monitor the HCl concentrations. It is shown that the rate constant values obtained in the study are 20-30 percent larger than those recommended by Smith and Zellner (1974) and Ravishankara et al. (1977) for modeling of stratospheric chemistry.

Molina, M. J.↗