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At least 325 records · Page 18

Oxidative Functionalization of Long-Chain Liquid Alkanes by Pulsed Plasma Discharges at Atmospheric Pressure

In this work, we introduce the oxidation of long aliphatic alkanes using non-thermal, atmospheric plasma processing as an eco-friendly route for organic synthesis. A pulsed dielectric barrier discharge in He/O 2 gas mixtures was employed to functionalize n-octadecane. C 18 secondary alcohols and ketones were the main products, with an optimal molar yield of ~29.2%. Prolonged treatment resulted in the formation of dialcohols, diketones, and higher molecular weight oxygenates. Lighter hydrocarbon products and decarboxylation to CO 2 were also observed at longer treatment times and higher power inputs. A maximum energy yield of 5.48 × 10 –8 mol/J was achieved at short treatment times and high powers, associated with higher selectivity to primary oxygenates. Direct hydroxylation of alkyl radicals, as well as disproportionation reactions, are proposed as the main pathways to alcohols and ketones. The results hold promise for functionalizing long hydrocarbon molecules at ambient conditions using catalyst-free plasma discharges.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Radio-Frequency Plasma Cleaning of a Penning Malmberg Trap

Radio-frequency-generated plasma has been demonstrated to be a promising means of cleaning the interior surfaces of a Penning-Malmberg trap that is used in experiments on the confinement of antimatter. {Such a trap was reported in Modified Penning-Malmberg Trap for Storing Antiprotons (MFS-31780), NASA Tech Briefs, Vol. 29, No. 3 (March 2005), page 66.} Cleaning of the interior surfaces is necessary to minimize numbers of contaminant atoms and molecules, which reduce confinement times by engaging in matter/antimatter-annihilation reactions with confined antimatter particles. A modified Penning-Malmberg trap like the one described in the cited prior article includes several collinear ring electrodes (some of which are segmented) inside a tubular vacuum chamber, as illustrated in Figure 1. During operation of the trap, a small cloud of charged antiparticles (e.g., antiprotons or positrons) is confined to a spheroidal central region by means of a magnetic field in combination with DC and radiofrequency (RF) electric fields applied via the electrodes. In the present developmental method of cleaning by use of RF-generated plasma, one evacuates the vacuum chamber, backfills the chamber with hydrogen at a suitable low pressure, and uses an RF-signal generator and baluns to apply RF voltages to the ring electrodes. Each ring is excited in the polarity opposite that of the adjacent ring. The electric field generated by the RF signal creates a discharge in the low-pressure gas. The RF power and gas pressure are adjusted so that the plasma generated in the discharge (see Figure 2) physically and chemically attacks any solid, liquid, and gaseous contaminant layers on the electrode surfaces. The products of the physical and chemical cleaning reactions are gaseous and are removed by the vacuum pumps.

Sims, William Herbert, III↗

Electron-impact excitation of the 3S0 and 5S0 states of atomic oxygen

The conditions of electron-impact excitation in flowing oxygen downstream from a discharge are reinterpreted. It is shown that total oxygen mass flow is not conserved as the discharge is turned on and off, even though the inlet flow rate remains constant. The total amount of gas is diminished when the discharge is turned on, apparently due to collection of atomic oxygen by the system walls. A revised total cross section is reported for the excitation of 1304-A radiation.

Stone, E. J.↗

Isotope dependence of the type I ELMy H-mode pedestal in JET-ILW hydrogen and deuterium plasmas

The pedestal structure, edge transport and linear MHD stability have been analyzed in a series of JET with the ITER-like wall hydrogen (H) and deuterium (D) type I ELMy H-mode plasmas. The pedestal pressure is typically higher in D than in H at the same input power and gas rate, with the difference mainly due to lower density in H than in D (Maggi et al (JET Contributors) 2018 Plasma Phys. Control. Fusion 60 014045). A power balance analysis of the pedestal has shown that higher inter-ELM separatrix loss power is required in H than in D to maintain a similar pedestal top pressure. This is qualitatively consistent with a set of interpretative EDGE2D-EIRENE simulations for H and D plasmas, showing that higher edge particle and heat transport coefficients are needed in H than in D to match the experimental profiles. It has also been concluded that the difference in neutral penetration between H and D leads only to minor changes in the upstream density profiles and with trends opposite to experimental observations. This implies that neutral penetration has a minor role in setting the difference between H and D pedestals, but higher ELM and/or inter-ELM transport are likely to be the main players. The interpretative EDGE2D-EIRENE simulations, with simultaneous upstream and outer divertor target profile constraints, have indicated higher separatrix electron temperature in H than in D for a pair of discharges at low fueling gas rate and similar stored energy (which required higher input power in H than in D at the same gas rate). The isotope dependence of linear MHD pedestal stability has been found to be small, but if a higher separatrix temperature is considered in H than in D, this could lead to destabilization of peeling-ballooning modes and shrinking of the stability boundary, qualitatively consistent with the reduced pedestal confinement in H.

08 HYDROGEN↗

Chondrule formation in lightning discharges

Chondrules represent a significant mass fraction of primitive meteorites. These millimeter-sized glassy droplets appear to be the products of intensive transient heating events. Their size distribution, chemical and mineral composition, texture, isotope composition suggest that chondrules were produced as a result of short-duration melting followed by rapid cooling of solid precursor particles. Gas-dynamics heating, magnetic reconnection, and electrostatic discharges are thought to be the leading candidates to explain chondrule formation. In this paper we summarize our recent theoretical progress on the effects of 'lightning' in the early solar system and also report on preliminary results from our laboratory experiments. Differential settling of various sized dust particles toward the midplane of the nebula is suspected to build large-scale charge separations that episodically relax via the electric breakdown of the nebular gas. The electrostatic discharge os analogous to lightning in the Earth's atmosphere.

Horanyi, M.↗

Demonstration of a new electrothermal thruster concept

The design and test of a microwave electrothermal thruster are described. The device, which employs a coaxial microwave discharge, was tested in nitrogen gas with 200-600 W of 2.45-GHz input power. Experimental measurements of thrust, specific impulse, and energy efficiency are presented for different flow and discharge pressures. Measured energy efficiencies varied between 30-60 percent and the performance compared favorably with other electrothermal thrusters operating in nitrogen gas. The experimental performance demonstrated the feasibility of the concept.

Whitehair, S.↗

Polynitrogen High Energy Density Materials Synthesized by Nonequilibrium Plasma

Metal pentazolate compounds that contain 5-nitrogen singly charged anion rings are an interesting class of materials from a thermodynamics perspective. These compounds are believed to be equilibrium phases only at extremely high pressures, and thus, they constitute exotic states of matter at ambient pressure and temperature. Moreover, the energy released by these pentazolate compounds upon relaxation to the equilibrium state at ambient conditions is in the range 1 to 10 MJ per kg, rivaling that of combustion reactions. The synthesis of pentazolates is not an easy task, and there are only two known methods, each of which has significant challenges. Here, the development of new scalable synthesis routes could enable the production of these exotic materials in sufficient quantity to explore their properties more widely beyond the context of explosives and propellants. In this Perspective, it is argued that nonequilibrium plasma is a promising reaction medium for the synthesis of metal pentazolate compounds, for example from the corresponding metal azide and N 2 gas activated by the discharge at low background temperature.

Chemical reactions↗

Reducing static charges in fluidized bed reactions

Radio frequency glow discharge apparatus ionizes fluidizing gas, making it conductive enough to neutralize static charge on fluidized particles. Particles agglomerate less, and in one case reactant loading capacity was increased six fold.

Wydeven, T.↗

Controlling Metal-Halide Vapor Density in Lasers

Streams of buffer gas convect and dilute metal-halide vapor. Technique uses flow of buffer gas through reservoir, which contains heated metal halide, to convect vapors into discharge tube. Second stream of buffer gas dilutes vapor. Final vapor density in laser tube controlled and changed by adjusting either one or both of buffer gas flow rates.

Pivirotto, T. J.↗

Covering solid, film cooled surfaces with a duplex thermal barrier coating

Thermal barrier coating systems were applied to hardware having passageways in the walls connecting apertures in the surface to a gas supply for film cooling. An inert gas, such as argon, is discharged through the apertures during the application of the thermal barrier coating system by plasma spraying. This flow of inert gas reduces both blocking of the holes and base metal oxidation during the coating operation.

Liebert, C. H.↗

On the abiotic formation of amino acids. I - HCN as a precursor of amino acids detected in extracts of lunar samples. II - Formation of HCN and amino acids from simulated mixtures of gases released from lunar samples

Two studies on the abiotic formation of amino acids are presented. The first study demonstrates the role of hydrogen cyanide as a precursor of amino acids detected in extracts of lunar samples. The formation of several amino acids, including glycine, alanine, aspartic acid, and glutamic acid, under conditions similar to those used for the analysis of lunar samples is demonstrated. The second study investigates the formation of hydrogen cyanide as well as amino acids from lunar-sample gas mixtures under electrical discharge conditions. These results extend the possibility of synthesis of amino acids to planetary bodies with primordial atmospheres less reducing than a mixture of methane, ammonia, hydrogen and water.

Yuasa, S.↗

Laboratory detection of a new interstellar free radical CH2CN(2B1)

An asymmetric-top free radical CH2CN with a 2B1 ground state was detected by laboratory microwave spectroscopy. The radical was produced in a free-space absorption cell by a DC glow discharge in pure CH3CN gas. About 60 fine-structure components were observed for the N = 11-10 to 14-13 a-type rotational transitions in the frequency region of 220-260 GHz. Hyperfine resolved components for the N = 4-3 and 5-4 transitions were resolved in the 80 and 100 GHz regions, respectively. Molecular constants were determined and U100602 and U80484 from Sgr B2, and U40240 and U20120 from TMC-1 were assigned to the N = 5-4, 4-3, 2-1, and 1-0 transitions with K(-1) = 0 of the CH2CN radical.

Saito, Shuji↗

Using EPSAT to analyze high power systems in the space environment

The authors review the Environment Power System Analysis Tool (EPSAT) design and demonstrate its capabilities by using it to address some questions that arose in designing the SPEAR III experiment. It is shown that that the rocket body cannot be driven to large positive voltages under the constraints of this experiment. Hence, attempts to measure the effects of a highly positive rocket body in the plasma environment should not be made in this experiment. It is determined that a hollow cathode will need to draw only about 50 mA to ground the rocket body. It is shown that a relatively small amount of gas needs to be released to induce a bulk breakdown near the rocket body, and this gas release should not discharge the sphere. Therefore, the experiment provides an excellent opportunity to study the neutralization of a differential charge.

Kuharski, Robert A.↗

A microwave plasma cleaning apparatus

In a microwave electron cyclotron resonance plasma source, reactive plasmas of oxygen and its mixtures of argon have been used for evaluating plasma cleaning technologies. Small aluminum samples (0.95 x 1.9 cm) were coated with thin films (less than or equal to 20 micrometers in thickness) of Shell Vitrea oil and cleaned with reactive plasmas. The discharge parameters, such as gas pressure, magnetic field, substrate biasing, and microwave power, were varied to change cleaning conditions. A mass spectroscopy (or residual gas analyzer) was used to monitor the status of plasma cleaning. Mass loss of the samples after plasma cleaning was measured to estimate cleaning rates. Measured cleaning rates of low-pressure (0.5-m torr) argon/oxygen plasmas were as high as 2.7 micrometers/min. X-ray photoelectron spectroscopy was used to determine cleanliness of the sample surfaces. In this paper, significant results of the plasma cleaning are reported and discussed.

Tsai, C. C.↗

Exploring the Fate of Nitrogen Heterocycles in Complex Prebiotic Mixtures

A long standing question in the field of prebiotic chemistry is the origin of the genetic macromolecules DNA and RNA. DNA and RNA have very complex structures with repeating subunits of nucleotides, which are composed of nucleobases (nitrogen heterocycles) connected to sugar-phosphate. Due to the instability of some nucleobases (e.g. cytosine), difficulty of synthesis and instability of D-ribose, and the likely scarcity of polyphosphates necessary for the modern nucleotides, alternative nucleotides have been proposed for constructing the first genetic material. Thus, we have begun to investigate the chemistry of nitrogen heterocycles in plausible, complex prebiotic mixtures in an effort to identify robust reactions and potential alternative nucleotides. We have taken a complex prebiotic mixture produced by a spark discharge acting on a gas mixture of N2, CO2, CH4, and H2, and reacted it with four nitrogen heterocycles: uracil, 5-hydroxymethyluracil, guanine, and isoxanthopterin (2-amino-4,7-dihydroxypteridine). The products of the reaction between the spark mixture and each nitrogen heterocycle were characterized by liquid chromatography coupled to UV spectroscopy and Orbitrap mass spectrometry. We found that the reaction between the spark mixtUl'e and isoxanthopterin formed one major product, which was a cyanide adduct. 5-hydroxymethyluracil also reacted with the spark mixture to form a cyanide adduct, uracil-5-acetonitrile, which has been synthesized previously by reacting HCN with S-hydroxymethyluracil. Unlike isoxanthopterin, the chromatogram of the 5-hydroxymethyluracil reaction was much more complex with multiple products including spark-modified dimers. Additionally, we observed that HMU readily self-polymerizes in solution to a variety of oligomers consistent with those suggested by Cleaves. Guanine and uracil, the biological nucleobases, did not react with the spark mixture, even at high temperature (100 C). This suggests that there are alternative nucleobases which are more reactive under prebiotic conditions and may have been involved in producing precursor nucleotides.

Smith, Karen E.↗

Examination of Annular-Electrode Spark Discharges in Flowing Oxygen - An Overview

A parametric study of annular spark gaps, pressures, and spark discharges in flowing oxygen gas was performed with a Champion spark exciter. The range of the pressure-distance product for the experiment is from approximately 50 torr-cm to 2500 torr-cm. Measurements of breakdown voltage qualitatively trend with Paschen's curve. Spark duration remained constant until the pressure-distance product exceeded 200 torr-cm, and then steadily increased. The mean spark energy increases linearly with the pressure-distance on a log-log plot indicating that a definite power relationship exists. The distribution of sparks at low energies and low pressures is not Gaussian and has no dominant peaks. Moderate and high spark energies are bimodal, with the dominant mode near 80 mJ. As pressure increases, dominant and secondary modes approach the same probability.

Darren C. Tinker↗

Formation of Amino Acids and Carboxylic Acids in Weakly Reducing Planetary Atmospheres by Solar Energetic Particles from the Young Sun

Life most likely started during the Hadean Eon; however, the environmental conditions which contributed to the complexity of its chemistry are poorly known. A better understanding of various environmental conditions, including global (heliospheric) and local (atmospheric, surface, and oceanic), along with the internal dynamic conditions of the early Earth, are required to understand the onset of abiogenesis. Herein, we examine the contributions of galactic cosmic rays (GCRs) and solar energetic particles (SEPs) associated with superflares from the young Sun to the formation of amino acids and carboxylic acids in weakly reduced gas mixtures representing the early Earth’s atmosphere. We also compare the products with those introduced by lightning events and solar ultraviolet light (UV). In a series of laboratory experiments, we detected and characterized the formation of amino acids and carboxylic acids via proton irradiation of a mixture of carbon dioxide, methane, nitrogen, and water in various mixing ratios. These experiments show the detection of amino acids after acid hydrolysis when 0.5% (v/v) of initial methane was introduced to the gas mixture. In the set of experiments with spark discharges (simulation of lightning flashes) performed for the same gas mixture, we found that at least 15% methane was required to detect the formation of amino acids, and no amino acids were detected in experiments via UV irradiation, even when 50% methane was used. Carboxylic acids were formed in non-reducing gas mixtures (0% methane) by proton irradiation and spark discharges. Hence, we suggest that GCRs and SEP events from the young Sun represent the most effective energy sources for the prebiotic formation of biologically important organic compounds from weakly reducing atmospheres. Since the energy flux of space weather, which generated frequent SEPs from the young Sun in the first 600 million years after the birth of the solar system, was expected to be much greater than that of GCRs, we conclude that SEP-driven energetic protons are the most promising energy sources for the prebiotic production of bioorganic compounds in the atmosphere of the Hadean Earth.

Kensei Kobayashi↗