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At least 181 records · Page 10

Classical trajectory studies of gas phase reaction dynamics and kinetics using ab initio potential energy surfaces

Strategies for constructing global potential energy surfaces from a limited number of accurate ab initio electronic energy calculations are discussed. Generally, these data are concentrated in small regions of configuration space (e.g., in the vicinity of saddle points and energy minima) and difficulties arise in generating a potential function that is globally well-behaved. Efficient computer codes for carrying out classical trajectory calculations on vector and parallel processors are also described. Illustrations are given from recent work on the following chemical systems: Ca + HF yields CaF + H, H + H + H2 yields H2 + H2, N + O2 yields NO + O and O + N2 yields NO + N. The dynamics and kinetics of metathesis, dissociation, recombination, energy transfer and complex formation processes will be discussed.

Jaffe, Richard L.↗

Gas-phase measurements of combustion interaction with materials for radiation-cooled chambers

Foil samples of Ir and Pt are exposed to combustion products in a controlled premixed environment at atmospheric pressure. Electrical heating of the foil samples is used to control the surface temperature and to elevate it above the radiative equilibrium temperature within the test apparatus. Profiles of temperature and OH concentration in the boundary layer adjacent to the specimen surface are measured by laser-induced fluorescence. Measured OH concentrations are significantly higher than equilibrium concentrations calculated for the known mixture ratio and the measured temperature profiles. This result indicates that superequilibrium concentrations of H-atoms and O-atoms are also present in the boundary layer, due to partial equilibrium of the rapid binary reactions of the H2/O2 chemical kinetic system. These experiments are conducted as part of a research program to investigate fundamental aspects of the interaction of combustion gases with advanced high-temperature materials for radiation-cooled thrusters.

Barlow, R. S.↗

Interstellar gas phase abundance of carbon, oxygen, nitrogen, copper, gallium, germanium, and krypton toward Zeta Ophiuchi

An analysis of weak (less than 10 mA) UV interstellar absorption line data obtained for the line of sight to the O9.5 IV star Zeta Oph is presented. Measurements of weak semiforbidden lines of N I, O I, Cu II, and a new UV detection of Na I are reported along with a small upper limit for C II. Interstellar detections of Ga II, Ge II, and Kr I are also presented. Ga, Ge, and Kr represent the heaviest elements detected in the ISM. A comparison of the derived column densities to cosmic abundances shows Ga to be depleted by about -1.2 dex while Ge is overabundant by +0.2 dex. Assuming Kr to be undepleted, a logarithmic cosmic abundance of Kr/H = 2.95 is obtained on the scale where H = 12.00.

Cardelli, Jason A.↗

Thermal degradation events as health hazards - Particle vs gas phase effects, mechanistic studies with particles

Experiments on animal subjects are performed to demonstrate that significant lung injury can result from the inhalation of ultrafine TiO2 or Al2O3 particles. The methods include intratracheal instillation of particles, long-term inhalation of particles, and in vitro studies of alveolar macrophages (AMs) to study the production of fibroplast growth factors. The ultrafine TiO2 particles are shown to induce more acute inflammatory reactions than larger particles and lead to persistent chronic effects in the AM-mediated clearance function of particles. The ultrafine particles also induce cytokines more readily, and the data generally suggests that the occurrence of such particles in thermal degradation events makes the fumes highly toxic. The exposure to thermal degradation products is therefore a critical concern for manned space missions with potentially degradable plastic products.

Oberdoerster, G.↗

A computer model for one-dimensional mass and energy transport in and around chemically reacting particles, including complex gas-phase chemistry, multicomponent molecular diffusion, surface evaporation, and heterogeneous reaction

Various chemically reacting flow problems highlighting chemical and physical fundamentals rather than flow geometry are presently investigated by means of a comprehensive mathematical model that incorporates multicomponent molecular diffusion, complex chemistry, and heterogeneous processes, in the interest of obtaining sensitivity-related information. The sensitivity equations were decoupled from those of the model, and then integrated one time-step behind the integration of the model equations, and analytical Jacobian matrices were applied to improve the accuracy of sensitivity coefficients that are calculated together with model solutions.

Cho, S. Y.↗

Principles of gas phase processing of ceramics during combustion

In recent years, ceramic materials have found applications in an increasingly wider range of industrial processes, where their unique mechanical, electrical and optical properties are exploited. Ceramics are especially useful for applications in high temperature, corrosive environments, which impose particularly stringent requirements on mechanical reliability. One approach to provide such materials is the manufacture of submicron (and more recently nanometer scale) particles, which may subsequently be sintered to produce a material with extremely high mechanical integrity. However, high quality ceramic materials can only be obtained if particles of known size, polydispersity, shape and chemical purity can be produced consistently, under well controlled conditions. These requirements are the fundamental driving force for the renewed interest in studying particle formation and growth of such materials.

Zachariah, Michael R.↗

Gas phase hydrogen permeation in a Ni-Fe-Co superalloy

Hydrogen permeation measurements have been conducted for the Incoloy 909 Ni-Fe-Co superalloy via the 'membrane' technique, in which the gaseous hydrogen at the entrance of a thin membrane is transposed through the bulk to the exit side of the membrane, at 400-810 C; the pressure range explored was 2.7 x 10 exp 3 to 1.3 x 10 exp 5 N/sq m. The lattice hydrogen solubility of Incoloy 909 is found to be only weakly temperature-dependent. These results are compared with those obtained for Incoloy 903.

Shanabarger, Mickey R.↗

Thermophysical properties of gas phase uranium tetrafluoride

Thermophysical data of gaseous uranium tetrafluoride (UF4) are theoretically obtained by taking into account dissociation of molecules at high temperatures (2000-6000 K). Determined quantities include specific heat, optical opacity, diffusion coefficient, viscosity, and thermal conductivity. A computer program is developed for the calculation.

Watanabe, Yoichi↗

Observation of CN Z - X and B - X emissions in gas-phase collisions of fast O(3P) atoms with HCN

Studies of spacecraft surfaces in LEO have shown that CN(B - X) emission occurs when the spacecraft shuttle engine exhaust species collide with the atmosphere. A study of the reaction of fast O(3P) atoms with HCN under single-collision conditions is reported. The channels active in the hyperthermal energy regime are identified as CN(B 2Sigma(+) - X 2Sigma(+)) and CN(A 2Pi(i) - X 2Sigma(+)) transitions. The experimental B - X vibrational bands fit a synthetic spectrum of CN at a vibrational temperature of 7000 K and a rotational temperature of 2000 K. The CN(B - X) emission is observed when spacecraft shuttle-engine exhaust species collide with the atmosphere.

Orient, O. J.↗

Thermal decomposition of ethylpentaborane in gas phase

The thermal decomposition of ethylpentaborane at temperatures of 185 degrees to 244 degrees C is approximately a 1.5-order reaction. The products of the decomposition were hydrogen, methane, a nonvolatile boron hydride, and traces of decaborane. Measurements of the rate of decomposition of pentaborane showed that ethylpentaborane has a greater rate of decomposition than pentaborane.

Mcdonald, Glen E↗

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.↗

Observation of CH A (sup 2)Delta approaches X (sup 2)Pi(sub r) and B (sup 2)Sigma(sup -) approaches X (sup 2)Pi(sub r) emissions in gas-phase collisions of fast O((sup 3)P) atoms with acetylene

Optical emissions in single-collision, beam-beam reactions of fast (3-22 eV translational energy) O(P-3) atoms with C2H2 have been measured in the wavelength range 300-850 nm. Two features were observed, one with a peak wavelength at 431 nm, corresponding to the CH A (sup 2)Delta yields X (sup 2)Pi(sub r) transition, and a second weaker emission in the range 380-400 nm corresponding to the B (sup 2)Sigma(sup -) yields X (sup 2)Pi(sub r) transition. Both the A yields X and B yields X emissions were fit to a synthetic spectrum of CH(A) at a vibrational temperature T(sub v) of 10,000 K (0.86 eV) and a rotational temperature T(r) of approximately 5000 K (0.43 eV); and CH(B) to T(sub v) = 2500 K (0.22 eV) and T(sub r) = 1000 K (0.09 eV). The energy threshold for the A yields X emission was measured to be 7.3 +/- 0.4 eV (lab) or 4.5 +/- 0.2 eV (c.m.). This agrees with the energy threshold of 7.36 eV (lab) for the reaction O(P-3) + C2H2 yields CH(A) + HCO.

Orient, O. J.↗

Flow Tube Studies of Gas Phase Chemical Processes of Atmospheric Importance

The objective of this project is to conduct measurements of elementary reaction rate constants and photochemistry parameters for processes of importance in the atmosphere. These measurements are being carried out under temperature and pressure conditions covering those applicable to the stratosphere and upper troposphere, using the chemical ionization mass spectrometry turbulent flow technique developed in our laboratory.

Molina, Mario J.↗

Flow Tube Studies of Gas Phase Chemical Processes of Atmospheric Importance

The objective of this project is to conduct measurements of elementary reaction rate constants and photochemical parameters for processes of importance in the atmosphere. These measurements are being carried out under temperature and pressure conditions covering those applicable to the stratosphere and upper troposphere, using the chemical ionization mass spectrometry turbulent flow technique developed in our laboratory. The next section summarizes our research activities during the first year of the project, and the section that follows consists of the statement of work for the third year. Additional details concerning the projects listed in the statement of work were described in our original proposal.

Molina, Mario J.↗

Identification of Gas Phase PAHs in Absorption Towards Protostellar Sources

The infrared emission bands (also known as the UIR bands.) have recently been observed in absorption at 3.25 micrometers in the ices surrounding a few proto-stellar objects at 11.2 micrometers in MonR2, and at 6.2 micrometers towards two sources near the galactic center. The UIR bands have been observed in emission for many years, but identifying these bands has proven to be both difficult and contentious as no one has yet found a single material that provides a good match to the features. However, most investigators agree that some form of carbon-based material with aromatic bonds is the most likely candidate, and many arguments favor free molecules (polycyclic aromatic hydrocarbons, PAHs) as the carriers of at least the narrow emission bands. Since the emission arises not from a single molecule but from a family of molecules, identifying which PAHs are contributing to the infrared emission bands is difficult. The identification is further complicated by the fact that the emission at short wavelengths is dominated by small molecules while at long wavelengths it is dominated by large molecules. Thus, for example, the emission at 3.3 micrometers is from a different mix of molecules than those which produce the 11.2 micrometer band. To complicate matters further, the molecular mix includes both neutral and ionic species. In absorption, the same mixture of molecules contributes at all wavelengths and the molecules should be neutral, potentially simplifying comparisons with lab data. Also, absorption strengths measured in the lab are directly applicable to interstellar absorption bands without the need to model an emission spectrum of an unknown mixture of ionized and neutral PAHs. In this paper we show that a mixture of argon matrix isolated PAH molecules can reproduce the 3.25 micrometers absorption band seen in the ISO SWS spectra of four embedded Infrared sources, S140 IRS1, AFGL 2591, Elias 29, and AFGL 989. In section 2 we describe the ISO SWS data analysis and in section 3 discuss the results.

Bregman, Jesse D.↗

Gas-Phase Influence on Quasisteady "Liquid Flames" in Gravitational Fields

We consider the SHS (self-propagating high-temperature synthesis) process for synthesizing materials. In this process a powder mixture of reactants is cold pressed into a sample, which is ignited at one end. A high temperature combustion wave then propagates through the sample converting reactants to the desired product material. In this process, melting of some or all the components is often observed. Therefore, we study combustion waves propagating through a high caloricity inorganic powder mixture whose combustion temperature exceeds the melting temperatures of many components. The solid matrix is thus destroyed by the propagating combustion wave due to melting ahead of the reaction zone, and a liquid bath is formed which contains gaseous bubbles. The waves propagate in the presence of a gravitational field. Due to the effect of gravity, there is relative motion between the rising bubbles and the descending bath, which affects the composition of the medium, its thermophysical properties, the 'liquid flame' structure, and the propagation velocity. To enhance our understanding of phenomena associated with the interaction of the relative motion with the propagating combustion wave we formulate and analyze a relatively simple mathematical model of liquid flames in a gravitational field. We describe the wave structure and combustion characteristics including the combustion velocity. We compare our results to existing experimental observations and suggest new experiments to be performed. We consider the effects of gravity and, in particular, examine both microgravity and large gravity conditions.

Shkadinsky, K. G.↗

Solid and Gas-Phase Spectroscopy of Cosmic Carbon Analogs: Results and Perspectives

The laboratory studies of interstellar carbon materials analogs (PAHs, Fullerenes, chains) will be discussed with their advantages and limitations from the point of view of the application to astrophysical processes. The discussion will focus on the newest generation of laboratory experiments that has been developed in order to provide a closer simulation of space environments and a better support to space missions. The astrophysical implications and future perspectives will be stressed.

Salama, Farid↗