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At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1989

Theoretical studies of the transition metal-carbonyl systems MCO and M(CO)2, M = Ti, Sc, and V

Large Gaussian basis sets and an electron correlation treatment are used in ab initio calculations on the transition metal-carbonyl systems MCO and N(CO)2 for M = Ti, Sc, and V. The results show that high-spin ground states are favored for the monocarbonyl molecules, and that for the dicarbonyl molecules there is a competition between high, intermediate, and low spin states which are very close in energy. Dissociation energies of 0.62 eV for Ti-CO and 1.02 for Ti(CO)2 are found, relative to the ground state Ti atomic asymptote and CO 1Sigma(+). The binding energy per carbonyl for the three metal atoms is shown to be significantly lower for the dicarbonyl than for the the monocarbonyl molecules.

Barnes, Leslie A.↗
NASA NTRS1994

Polyamideimides Containing Carbonyl And Ether Linkages

Polyamideimides of new class contain carbonyl and ether connecting groups. New polyamideimides more easily processable, stronger in tension, and more resistant to solvents (including water) than conventional polyamideimides. Improvements in mechanical and chemical properties attributable to semicrystallinity introduced into otherwise amorphous polymers by incorporation of carbonyl and ether linkages.

Hergenrother, Paul M.↗
NASA NTRS1993

An intercomparison of aircraft instrumentation for tropospheric measurements of carbonyl sulfide, hydrogen sulfide, and carbon disulfide

This paper reports results of NASA's Chemical Instrumentation and Test Evaluation (CITE 3) during which airborne measurements for carbonyl sulfide (COS), hydrogen sulfide (H2S), and carbon disulfide (CS2) were intercompared. Instrumentation included a gas chromatograph using flame photometric detection (COS, H2S, and CS2), a gas chromatograph using mass spectrometric detection (COS) and CS2), a gas chromatograph using fluorination and subsequent SF6 detection via electron capture (COS and CS2), and the Natusch technique (H2S). The measurements were made over the Atlantic Ocean east of North and South America during flights from NASA's Wallops Flight Center, Virginia, and Natal, Brazil, in August/September 1989. Most of the intercomparisons for H2S and CS2 were at mixing ratios less than 25 pptv and less than 10 pptv, respectively, with a maximum mixing ratio of about 100 pptv and 50 pptv, respectively. Carbonyl sulfide intercomparisons were at mixing ratios between 400 and 600 pptv. Measurements were intercompared from data bases constructed from time periods of simultaneous or overlapping measurements. Agreement among the COS techniques averaged about 5%, and individual measurements were generally within 10%. For H2S and at mixing ratio greater than 25 pptv, the instruments agreed on average to about 15%. At mixing ratios less than 25 pptv the agreement was about 5 pptv. For CS2 (mixing ratios less than 50 pptv), two techniques agreed on average to about 4 pptv, and the third exhibited a bias (relative to the other two) that varied in the range of 3-7 pptv. CS2 mixing ratios over the ocean east of Natal as measured by the gas chromatograph-mass spectrometer technique were only a few pptv and were below the detection limits of the other two techniques. The CITE 3 data are used to estimate the current uncertainty associated with aircraft measurements of COS, H2S, and CS2 in the remote troposphere.

Gregory, Gerald L.↗
NASA NTRS1993

Airborne measurements of sulfur dioxide, dimethyl sulfide, carbon disulfide, and carbonyl sulfide by isotope dilution gas chromatography/mass spectrometry

A gas chromatograph/mass spectrometer is described for determining atmospheric sulfur dioxide, carbon disulfide, dimethyl sulfide, and carbonyl sulfide from aircraft and ship platforms. Isotopically labelled variants of each analyte were used as internal standards to achieve high precision. The lower limit of detection for each species for an integration time of 3 min was 1 pptv for sulfur dioxide and dimethyl sulfide and 0.2 pptv for carbon disulfide and carbonyl sulfide. All four species were simultaneously determined with a sample frequency of one sample per 6 min or greater. When only one or two species were determined, a frequency of one sample per 4 min was achieved. Because a calibration is included in each sample, no separate calibration sequence was needed. Instrument warmup was only a few minutes. The instrument was very robust in field deployments, requiring little maintenance.

Bandy, Alan R.↗
NASA NTRS2011

A Theoretical Investigation of the Plausibility of Reactions Between Ammonia and Carbonyl Species (Formaldehyde, Acetaldehyde, and Acetone) in Interstellar Ice Analogs at Ultracold Temperatures

We have reexamined the reaction between formaldehyde and ammonia, which was previously studied by us and other workers in modestly sized cluster calculations. Larger model systems with up to 12H2O were employed, and reactions of two more carbonyl species, acetaldehyde and acetone, were also carried out. Calculations were performed at the B3LYP/6-31+G** level with bulk solvent effects treated with a polarizable continuum model; limited MP2/6-31+G** calculations were also performed. We found that while the barrier for the concerted proton relay mechanism described in previous work remains modest, it is still prohibitively high for the reaction to occur under the ultracold conditions that prevail in dense interstellar clouds. However, a new pathway emerged in more realistic clusters that involves at least one barrierless step for two of the carbonyl species considered here: ammonia reacts with formaldehyde and acetaldehyde to form a partial charge transfer species in small clusters (4H2O) and a protonated hydroxyamino intermediate species in large clusters (9H2O, 12H2O); modest barriers that decrease sharply with cluster size are found for the analogous processes for the acetone-NH3 reaction. Furthermore, if a second ammonia replaces one of the water molecules in calculations in the 9H2O clusters, deprotonation can occur to yield the same neutral hydroxyamino species that is formed via the original concerted proton relay mechanism. In at least one position, deprotonation is barrierless when zero-point energy is included. In addition to describing the structures and energetics of the reactions between formaldehyde, acetaldehyde, and acetone with ammonia, we report spectroscopic predictions of the observable vibrational features that are expected to be present in ice mixtures of different composition.

Chen, Lina↗
NASA NTRS1974

Absolute rate parameters for the reaction of ground state atomic oxygen with carbonyl sulfide

The rate parameters for the reaction of O(3P) with carbonyl sulfide, O(3P) + OCS yields CO + SO, have been determined directly by monitoring O(3P) using the flash photolysis-resonance fluorescence technique. The value for reaction rate was measured over a temperature range of 263-502 K and the data were fitted to an Arrhenius expression with good linearity. A comparison of the present results with those from previous studies of this reaction is also presented.

Klemm, R. B.↗
NASA NTRS1981

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.↗
NASA NTRS1981

Temperature dependent UV absorption cross sections for carbonyl sulfide

The ultraviolet absorption spectrum of carbonyl sulfide is investigated in order to assess the importance of the photolytic sink for OCS in the troposphere. Absorption cross sections were measured at wavelengths between 185 and 300 nm in a double-beam spectrometer at temperatures of 295 and 225 K. The results are found to be in good agreement with previous reports in the short wavelength region, but significantly lower than the value of 2 x 10 to the 22nd sq cm/molecule proposed by Rudolf and Inn (1981) between 280 and 300 nm, which may be attributed to trace contaminants or dimerization. A marked temperature effect is noted at wavelengths greater than 240 nm and below 190 nm. As no evidence of absorption at wavelengths greater than 270 nm was found, estimates of the solar photodissociation rate of tropospheric OCS based on the present cross sections yield a value of about 2 x 10 to the -9th/sec, corresponding to a tropospheric lifetime of about 20 years. It is therefore concluded that solar photolysis represents a negligible sink for OCS.

Molina, L. T.↗
NASA NTRS1984

The metal-carbonyl bond in Ni(CO)4 and Fe(CO)5 - A clear-cut analysis

A detailed analysis of the metal-carbonyl bonding in Ni(CO)4 and Fe(CO)5, based on the newly developed contained space orbital variation (CSOV) method, is carried out to investigate various contributing factors to the interaction. Three aspects about the metal-CO interaction are presented: (1) the frozen orbital repulsion between the metal 4s and the CO is large; (2) the metal to CO pi donation is energetically much more important than the CO to the metal sigma donation; and (3) the metal 4s and 4p orbitals make a very small contribution (smaller than 0.4 eV) to the interaction energy; the largest portion of this contribution arises from the CO to metal sigma donation.

Bauschlicher, C. W., Jr.↗
NASA NTRS1987

Polyimides Containing Carbonyl and Ether Connecting Groups

Semicrystallinity gives rise to tough, solvent-resistant polymers. New polyimides prepared from reaction of aromatic dianhydrides with new diamines containing carbonyl and ether connecting groups between aromatic rings. Damines prepared from reaction of 4-aminophenol with activated aromatic difluoro compounds in presence of potassium carbonate. These types of polymers have potential applications in molded products, films, adhesives, and composites.

Hergenrother, Paul M.↗
NASA NTRS1986

Detection of carbonyl fluoride in the stratosphere

Infrared solar absorption spectra of the stratosphere recorded at a resolution of 0.01/cm by the ATMOS (Atmospheric Trace Molecule Spectroscopy) instrument from onboard Spacelab 3 (04/30 to 05/6/85) have revealed the existence of many previously unobserved absorption features in the 1925 to 1960/cm and 1249 to 1255/cm regions and one at 774/cm. On the basis of comparisons with laboratory spectra, these features have been identified as belonging to the nu1, nu4, and nu6 bands of carbonyl fluoride, respectively. Volume mixing ratios of COF2 between 17 and 40 km have been deduced from analysis of the nu1 and nu6 bands.

Rinsland, C. P.↗