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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
NASA NTRS2017

Thermal Studies of Ammonium Cyanide Reactions: A Model for Thermal Alteration of Prebiotic Compounds in Meteorite Parent Bodies

Organic compounds in carbonaceous chondrites were likely transformed by a variety of parent body processes including thermal and aqueous processing. Here, we analyzed ammonium cyanide reactions that were heated at different temperatures and times by multiple analytical techniques. The goal of this study is to better understand the effect of hydrothermal alteration on cyanide chemistry, which is believed to be responsible for the abiotic synthesis of purine nucleobases and their structural analogs detected in carbonaceous chondrites.

Hammer, P. G.↗
NASA NTRS1996

The Submillimeter-Wave Spectrum of Isotopic Methyl Cyanide

The laboratory submillimeter-wave rotational spectrum of the 13 CH 3 CN, CH 3 13 CN, and the CH 3 C 15 N isotopomers of methyl cyanide has been observed in natural abundance in the 294 to 607 GHz region. The maximum J and K values are 34 an 14, respectively. Fifteen additional CH 3 CN transitions up to K=21 were also measured. The transitions of all four species are fitted to a symmetric top Hamiltonian and the rotation and distortion constants are determined. The 14 N quadropole and spin rotation are also calculated and presented. Suggested values for many other parameters which could not be directly determined from the isotope spectra are calculated from the normal species values and isotope relationships. The determined and calculated constants should predict the spectrum of the three isotopomers to well over 1 THz accurately enough for astronomical assignments.

methyl↗
DOE OSTI2024

Catalytic Reduction of Cyanide to Ammonia and Methane at a Mononuclear Fe Site

Nitrogenase enzymes catalyze nitrogen reduction (N 2 R) to ammonia and also the reduction of non-native substrates, including the 7H + /6e – reduction of cyanide to CH 4 and NH 3 . CN – and N 2 are isoelectronic, and it is hence fascinating to compare the mechanisms of synthetic Fe catalysts capable of both CN – and N 2 reduction. Here, we describe the catalytic reduction of CN – to NH 3 and CH 4 by a highly selective (P 3 Si )Fe(CN) catalyst (P 3 Si represents a tris(phosphine)silyl ligand). Catalysis is driven in the presence of excess acid ([Ph 2 NH 2 ]OTf) and reductant ((C 6 H 6 ) 2 Cr), with turnover as high as 73 demonstrated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Elucidating the mechanism of photochemical CO 2 reduction to CO using a cyanide-bridged di-manganese complex

The complex, [{[Mn(bpy)(CO) 3 ] 2 }(μ-CN)] + (Mn 2 CN + ), has previously been shown to photochemically reduce CO 2 to CO. The detailed mechanism behind its reactivity was not elucidated. In this work, the photoevolution of this reaction is studied in acetonitrile (MeCN) using IR and UV-vis spectroscopy. Samples were excited into the Mn I → π* bpy metal-to-ligand charge transfer (MLCT) absorption band triggering CO loss, and rapid MeCN solvent ligation at the open coordination site. It is concluded that this process occurs selectively at the Mn axial ligation site that is trans to the C-end of the bridging cyanide. Upon further photolysis, the metal–metal bonded dimeric species, [(CO) 3 (bpy)Mn–Mn(bpy)(CO) 3 ] (Mn–Mn) is observed to form under anaerobic conditions. The presence of this dimeric species coincides with the observation of CO production. When oxygen is present, CO 2 photoreduction does not occur, which is attributed to the inability of Mn 2 CN + to convert to the metal–metal bonded dimer. Photolysis experiments, where the Mn–Mn dimer is formed photochemically under argon first and then exposed to CO 2 , reveal that it is the radical species, [Mn(bpy)(CO) 3 ˙] (Mn˙), that interacts with the CO 2 . Since the presence of Mn–Mn and light is required for CO production, [Mn(bpy)(CO) 3 ˙] is proposed to be a photochemical reagent for the transformation of CO 2 to CO.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Laser-Plasma Spatiotemporal Cyanide Spectroscopy and Applications

This article reports new measurements of laser-induced plasma hypersonic expansion measurements of diatomic molecular cyanide (CN). Focused, high-peak-power 1064 nm Q-switched radiation of the order of 1 TW/cm 2 generated optical breakdown plasma in a cell containing a 1:1 molar gas mixture of N 2 and CO 2 at a fixed pressure of 1.1 × 10 5 Pascal and in a 100 mL/min flow of the mixture. Line-of-sight (LOS) analysis of recorded molecular spectra indicated the outgoing shockwave at expansion speeds well in excess of Mach 5. Spectra of atomic carbon confirmed increased electron density near the shockwave, and, equally, molecular CN spectra revealed higher excitation temperature near the shockwave. Results were consistent with corresponding high-speed shadowgraphs obtained by visualization with an effective shutter speed of 5 nanoseconds. In addition, LOS analysis and the application of integral inversion techniques allow inferences about the spatiotemporal plasma distribution.

36 MATERIALS SCIENCE↗
NASA NTRS1976

Formation of amino acids by cobalt-60 irradiation of hydrogen cyanide solutions

Experiments were conducted to study the pathway for the prebiotic origin of amino acids from hydrogen cyanide (HCN) under the action of ionizing radiation considered as an effective source of energy on the primitive earth. The irradiations were performed in a cobalt-60 source with a dose rate of 200,000 rad/hr. Seven naturally occurring amino acids are identified among the products formed by the hydrolysis of gamma-irradiated solutions of HCN: glycine, alanine, valine, serine, threonine, aspartic acid, and glutamic acid. The identity of these amino acids is established by gas chromatography and mass spectrometry. Control experiments provided evidence that the amino acids are not the result of contamination.

Sweeney, M. A.↗
NASA NTRS1978

A new channel for the formation of hydrogen cyanide in CH2-N2 systems

The reaction between N2 and either the singlet or the triplet electronic state of CH2 is investigated in order to shed light on the formation of NO in fuel-rich hydrocarbon flames. For the reaction of N2 and the triplet CH2, a rate constant less than or equal to 10 to the minus 16th power cu cm/molecule-sec is obtained. The time history of hydrogen cyanide production from the CH2-N2 systems is discussed as a basis for understanding the possible reaction routes from HCN to NO.

Laufer, A. H.↗
NASA NTRS1977

The effects of the pollutant, sodium cyanide, on the morphology and physiology of oedogonium cardiacum

OEDOGONIUM cardiacum exposed to varying concentrations of sodium cyanide for 15 day periods exhibited both morphological and physiological alterations. Organisms were exposed to the pollutant in concentrations of 1, 10, 25, 50, and 100 parts per million. Exposure period for organisms in each concentration was 15 days. As the concentration of the pollutant increased fragmentation also increased. Exposure also caused organisms to lose chlorophyll. The third morphological alteration was the incidence of rupture. Physiological effects altered by exposure included: reduced oxygen evolution, retardation of starch production and death. Death occurs when organisms are exposed to high concentrations over the total 15 day period.

Sparks, E.↗
NASA NTRS1978

Chemical evolution. XXIX - Pyrimidines from hydrogen cyanide

Compounds obtained by hydrolysis of HCN oligomers formed by allowing pH 9.2, 0.1 M cyanide to stand at room temperature for 4 to 12 months were analyzed. Hydrolysis of HCN oligomers yielded 4,5-dihydroxypyrimidine and 5-hydroxyuracil; orotic acid was detected after hydrolysis at pH 8.5. A unified pathway from diaminofumaronitrile to the pyrimidines observed is suggested. As purines, pyrimidines and amino acids are released by hydrolysis of HCN oligomers in either acidic or mildly basic aqueous solutions, they could have been formed on the primitive earth in spite of fluctuations in pH. 4,5-dihydroxypyrimidines appear to be likely candidates for incorporation into primitive nucleic acids, as they should undergo Watson-Crick hydrogen bonding with adenine.

Ferris, J. P.↗
NASA NTRS1982

Ground-based infrared spectroscopic measurements of atmospheric hydrogen cyanide

A number of lines of the nu-3 band of hydrogen cyanide have been detected in solar absorption spectra recorded near sunrise and sunset at Kitt Peak National Observatory (elevation 2095 m) with a 0.01/cm resolution Fourier transform spectrometer. Analysis of two of the strongest and best isolated lines has led to a value of 2.73 x 10 to the 15th molecules/sq cm for the vertical column abundance of HCN above Kitt Peak. The accuracy of this value is estimated as + or - 25%. This result, combined with the stratospheric concentration of HCN derived by Coffey, Mankin, and Cicerone (1981), yields 166 parts per trillion by volume for the average mixing ratio of HCN between 2 and 12 km. This is the first determination of the HCN concentration in the nonurban troposphere.

Rinsland, C. P.↗