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At least 163 records · Page 9

Gas-phase hydrogen permeation through alpha-titanium - Surface film and dimensional effects

The two techniques normally used to determine diffusivity and permeability in metals are considered and a description is presented of experiments which had been conducted to determine the direct effect of oxide and nitride films on the membrane surface as a function of location and thickness. The test specimens used in the experiments has been machined from commercially pure titanium rod. The results of the experiments show that hydrogen transport in alpha-titanium is partially or completely controlled by surface reactions depending upon membrane wall thickness and the composition and thickness of the surface film.

Shah, K. K.↗

Analysis of torsional spectra of molecules with two internal C/3v/ rotors. III - Far-infrared and gas phase Raman spectra of dimethylamine-d0, -d3, and -d6

The Raman spectra of gaseous dimethylamine-d0, -d3, and -d6 have been recorded between 0 and 4000/cm. The far-infrared spectra have been recorded between 300 and 100/cm. Considerable torsional data are reported and used to characterize the torsional potential function based on a semi-rigid model. The average effective V3 for the dimethylamines was found to be 1052 plus or minus 12/cm. The cos-cos coupling term was approximately 15% of the effective V3, whereas the sine-sine coupling term was of an order of magnitude smaller for (CH3)2NH and (CD3)2NH. However, for the mixed isotope the sine-sine term was found to be negligible and the cos-cos about one-half the value obtained for the other two isotopes.

Durig, J. R.↗

New gas phase inorganic ion cluster species and their atmospheric implications

Recent experimental laboratory observations, with high-pressure mass spectroscopy, have revealed the existence of previously unreported species involving water clustered to sodium dimer ions, and alkali metal hydroxides clustered to alkali metal ions. The important implications of these results concerning the existence of such species are here discussed, as well as how from a practical aspect they confirm the stability of certain cluster species proposed by Ferguson (1978) to explain masses recently detected at upper altitudes using mass spectrometric techniques.

Maerk, T. D.↗

A model for gas phase chemistry in interstellar clouds. II - Nonequilibrium effects and effects of temperature and activation energies

The chemical evolution of diffuse and dense interstellar clouds is examined via the time-dependent model outlined by Prasad and Huntress (1980). This paper presents specific results for CH, CO, CH4, O2, CH2O, CN, C2, C2H, HC3N, and NH3. Comparison with observations and predictions of other contemporary models show that cloud temperature plays a very important role through the inverse temperature dependence of radiative association reactions and through activation energies in neutral reactions and selected ion-molecule reactions. The observed fractional abundance of CN with respect to H2 and more accurate recent laboratory data on CN + O and CN + O2 reactions suggest that there is an unidentified, yet efficient, mechanism for conversion of O and O2 into polyatomic species. C2H and HC3N are synthesized early in the history of dense clouds. The value of the fractional abundance of C2H remains high, because as the cloud cools down the activation energy in the C2H + O reaction closes down this most important loss channel. A rapidly decreasing fractional abundance of O with time can also accomplish the same result. The value of the fractional abundance of HC3N remains high because it is an unreactive molecule and probably does not condense readily onto grains.

Prasad, S. S.↗

Kinetics of the gas-phase reaction between hydroxyl and carbonyl sulfide over the temperature range 300-517 K

By use of a discharge-flow resonance-fluorescence method the rate constant for the title reaction has been measured at five temperatures in the range 300-520 K. The Arrhenius expression is k(OH + OCS) = (1.3 + or - 0.3) x 10 to the -12th exp/-(2300 + or - 100)/T/ cu cm/s. Mass spectrometry has been used to detect the product HS and to collect some information about its reactivity. This study has carefully avoided the pitfalls associated with possible photolysis of reactants and complications due to H2S impurity in carbonyl sulfide that may have marred previous studies. This study has confirmed that the rate constant for this reaction is so much lower than the value originally used in computer modeling of the upper and lower atmosphere that conclusions about the relative importance of photolysis of OCS and of the reaction OH + OCS in the stratosphere must now be reassessed. The reaction OH + OCS has little significance for atmospheric chemistry.

Leu, M.-T.↗

Deposition of thin insulation layers from the gas phase

The continuous deposition of thin organic dielectric films on metallized carrier foils by glow discharge in monomeric gases is described. Depending on the applied monomers, the films had a dissipation factor of .001 to .003 (1 kHz), a relative permittivity of 2.3 to 2.5 and a resistivity of about 10 to the 17th power omega cm. Additionally, they proved to have a high mechanical homogeneity. Self-healing rolled capacitors with a very high capacitance per volume and of consistently high quality were fabricated from the metallized carrier foils covered with the dielectric film.

Behn, R.↗

Studies of clusters in the gas phase and application to an understanding of transitions from gaseous to the surface and condensed state

Studies of the structure, stability, electronic properties, and formation kinetics of small clusters were reviewed which provide information useful in furthering understanding of nucleation processes, liquid state properties, and the nature of surfaces. Using mass spectrometric coupled with various high pressure ion clustering and Stark effect-molecular beam techniques, the details of the primary clustering steps leading to the nucleation of bulk liquid from the vapor were and obtained by direct observation results are presented.

Castleman, A. W., Jr.↗

Gas-phase hydrogen permeation through alpha-titanium - Surface film and dimensional effects

The process of hydrogen transport through alpha-Ti involves simultaneous diffusion and phase boundary reactions at both surfaces, with the relative effect on each surface depending on the extent of surface contamination as well as the physical dimensions of the titanium membrane used. It is shown by the present study that hydrogen permeation in commercially pure alpha-Ti increases exponentially with temperature and is dependent on the first power of the input pressure, whether the surface is as-polished, preoxidized or prenitrided. Permeation decreases in the case of the as-polished condition if nitride or oxide films are formed at the surface in contact with source hydrogen, while increasing slightly for the same condition if such films are formed at the hydrogen exit surface.

Shah, K. K.↗

Vibration-rotation line strengths of the gas-phase OH radical

Absorption line strengths have been measured at 295 K for the first time for four vibration-rotation transitions of the OH radical, using a tunable, infrared diode-laser in conjunction with a molecular modulation spectrometer. A periodically varying OH concentration was created by photolysis, using a sinusoidally modulated 2537-A Hg lamp, of a flowing mixture of O3 and H2O contained within a quartz-walled White cell. The modulated absorption owing to the OH radical was subsequently observed by phase-sensitive detection. The absolute modulation amplitude of the OH number density was obtained by numerical simulation of the complete time-dependent photochemical system. The strongest transition measured was at 3407.607 kaysers, with a strength of 3.3 + or - 1.5 x 10 to the -20th per(cm molecule) sq cm.

Podolske, J.↗

Stability and photochemistry of ClO dimers formed at low temperature in the gas phase

The recent observations of elevated concentrations of the ClO radical in the austral spring over Antarctica have implicated catalytic destruction by chlorine in the large depletions seen in the total ozone column. One of the chemical theories consistent with an elevated concentration of the ClO is a cycle involving the formation of the ClO dimer through the association reaction: ClO + ClO = Cl2O2 and the photolysis of the dimer to give the active Cl species necessary for O3 depletion. Here, researchers report experimental studies designed to characterize the dimer of ClO formed by the association reaction at low temperatures. ClO was produced by static photolysis of several different precursor systems: Cl sub 2 + O sub 3; Cl sub 2 O sub 2; OClO + Cl sub 2 O spectroscopy in the U.V. region, which allowed the time dependence of Cl sub 2, Cl sub 2 O, ClO, OClO, O sub 3 and other absorbing molecules to be determined.

Cox, R. A.↗

Body frame close coupling wave packet approach to gas phase atom-rigid rotor inelastic collisions

The close coupling wave packet (CCWP) method is formulated in a body-fixed representation for atom-rigid rotor inelastic scattering. For J greater than j-max (where J is the total angular momentum and j is the rotational quantum number), the computational cost of propagating the coupled channel wave packets in the body frame is shown to scale approximately as N exp 3/2, where N is the total number of channels. For large numbers of channels, this will be much more efficient than the space frame CCWP method previously developed which scales approximately as N-squared under the same conditions.

Sun, Y.↗

CI, CII, and CO as tracers of gas phase carbon

In the dense interstellar medium, we find that about 20 percent of the total carbon abundance is in the form of CO, about 3 percent in C(sub I), and 100 percent in C(sub II) with uncertainties of factors of order 2. The abundance of other forms of gaseous carbon is negligible. CO is widespread throughout molecular clouds as is C(sub I). C(sub II) has only been observed near bright star-formation regions so far because of its high excitation energy. Further from ultraviolet sources it may be less abundant. Altogether we have accounted for about 1/3 of the total carbon abundance associated with dense molecular clouds. Since the other gaseous forms are thought to have negligible abundances, the rest of the carbon is probably in solid form.

Keene, Jocelyn↗