Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Gas phase”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Gas-Phase Hydrogen-Atom Measurement above Catalytic and Noncatalytic Materials during Ethane Dehydrogenation

The role of a solid surface for initiating gas-phase reactions is still not well understood. The hydrogen atom (H) is an important intermediate in gas-phase ethane dehydrogenation and is known to interact with surface sites on catalysts. However, direct measurements of H near catalytic surfaces have not yet been reported. Here, we present the first H measurements by laser-induced fluorescence in the gas-phase above catalytic and noncatalytic surfaces. Measurements at temperatures up to 700 °C show H concentrations to be at the highest above inert quartz surfaces compared to stainless steel and a platinum-based catalyst. Additionally, H concentrations above the catalyst decreased rapidly with time on stream. Furthermore, these newly obtained observations are consistent with the recently reported differences in bulk ethane dehydrogenation reactivity of these materials, suggesting H may be a good reporter for dehydrogenation activity.

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

How well do local relations predict gas-phase metallicity gradients? Results from SDSS-IV MaNGA

ABSTRACT Gas-phase metallicity gradients in galaxies provide important clues to those galaxies’ formation histories. Using SDSS-IV MaNGA data, we previously demonstrated that gas metallicity gradients vary systematically and significantly across the galaxy mass–size plane: at stellar masses beyond approximately $10^{10}\, \mathrm{M_\odot }$, more extended galaxies display steeper gradients (in units of dex/Re) at a given stellar mass. Here, we set out to develop a physical interpretation of these findings by examining the ability of local ∼kpc-scale relations to predict the gradient behaviour along the mass–size plane. We find that local stellar mass surface density, when combined with total stellar mass, is sufficient to reproduce the overall mass–size trend in a qualitative sense. We further find that we can improve the predictions by correcting for residual trends relating to the recent star formation histories of star-forming regions. However, we find as well that the most extended galaxies display steeper average gradients than predicted, even after correcting for residual metallicity trends with other local parameters. From these results, we argue that gas-phase metallicity gradients can largely be understood in terms of known local relations, but we also discuss some possible physical causes of discrepant gradients.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2020

Near-Surface Imaging of the Multicomponent Gas Phase above a Silver Catalyst during Partial Oxidation of Methanol

Fundamental chemistry in heterogeneous catalysis is increasingly explored using operando techniques in order to address the pressure gap between ultrahigh vacuum studies and practical operating pressures. Because most operando experiments focus on the surface and surface-bound species, there is a knowledge gap of the near-surface gas phase and the fundamental information the properties of this region convey about catalytic mechanisms. In this work, we demonstrate in situ visualization and measurement of gas-phase species and temperature distributions in operando catalysis experiments using complementary near-surface optical and mass spectrometry techniques. The partial oxidation of methanol over a silver catalyst demonstrates the value of these diagnostic techniques at 600 Torr (800 mbar) pressure and temperatures from 150 to 410 °C. Planar laser-induced fluorescence provides two-dimensional images of the formaldehyde product distribution that show the development of the boundary layer above the catalyst under different flow conditions. Raman scattering imaging provides measurements of a wide range of major species, such as methanol, oxygen, nitrogen, formaldehyde, and water vapor. Near-surface molecular beam mass spectrometry enables simultaneous detection of all species using a gas sampling probe. Detection of gas-phase free radicals, such as CH 3 and CH 3 O, and of minor products, such as acetaldehyde, dimethyl ether, and methyl formate, provides insights into catalytic mechanisms of the partial oxidation of methanol. The combination of these techniques provides a detailed picture of the coupling between the gas phase and surface in heterogeneous catalysis and enables parametric studies under different operating conditions, which will enhance our ability to constrain microkinetic models of heterogeneous catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1998

LSPRAY: Lagrangian Spray Solver for Applications With Parallel Computing and Unstructured Gas-Phase Flow Solvers

Sprays occur in a wide variety of industrial and power applications and in the processing of materials. A liquid spray is a phase flow with a gas as the continuous phase and a liquid as the dispersed phase (in the form of droplets or ligaments). Interactions between the two phases, which are coupled through exchanges of mass, momentum, and energy, can occur in different ways at different times and locations involving various thermal, mass, and fluid dynamic factors. An understanding of the flow, combustion, and thermal properties of a rapidly vaporizing spray requires careful modeling of the rate-controlling processes associated with the spray's turbulent transport, mixing, chemical kinetics, evaporation, and spreading rates, as well as other phenomena. In an attempt to advance the state-of-the-art in multidimensional numerical methods, we at the NASA Lewis Research Center extended our previous work on sprays to unstructured grids and parallel computing. LSPRAY, which was developed by M.S. Raju of Nyma, Inc., is designed to be massively parallel and could easily be coupled with any existing gas-phase flow and/or Monte Carlo probability density function (PDF) solver. The LSPRAY solver accommodates the use of an unstructured mesh with mixed triangular, quadrilateral, and/or tetrahedral elements in the gas-phase solvers. It is used specifically for fuel sprays within gas turbine combustors, but it has many other uses. The spray model used in LSPRAY provided favorable results when applied to stratified-charge rotary combustion (Wankel) engines and several other confined and unconfined spray flames. The source code will be available with the National Combustion Code (NCC) as a complete package.

Raju, Manthena S.↗
NASA NTRS2006

Laboratory Studies on the Formation of Carbon-Bearing Molecules in Extraterrestrial Environments: From the Gas Phase to the Solid State

A detailed knowledge of the formation of carbon-bearing molecules in interstellar ices and in the gas phase of the interstellar medium is of paramount interest to understand the astrochemical evolution of extraterrestrial environments (1). This research also holds strong implications to comprehend the chemical processing of Solar System environments such as icy planets and their moons together with the atmospheres of planets and their satellites (2). Since the present composition of each interstellar and Solar System environment reflects the matter from which it was formed and the processes which have changed the chemical nature since the origin (solar wind, planetary magnetospheres, cosmic ray exposure, photolysis, chemical reactions), a detailed investigation of the physicochemical mechanisms altering the pristine environment is of paramount importance to grasp the contemporary composition. Once these underlying processes have been unraveled, we can identify those molecules, which belonged to the nascent setting, distinguish molecular species synthesized in a later stage, and predict the imminent chemical evolution of, for instance, molecular clouds. Laboratory experiments under controlled physicochemical conditions (temperature, pressure, chemical composition, high energy components) present ideal tools for simulating the chemical evolution of interstellar and Solar System environments. Here, laboratory experiments can predict where and how (reaction mechanisms; chemicals necessary) in extraterrestrial environments and in the interstellar medium complex, carbon bearing molecules can be formed on interstellar grains and in the gas phase. This paper overviews the experimental setups utilized in our laboratory to mimic the chemical processing of gas phase and solid state (ices) environments. These are a crossed molecular beams machine (3) and a surface scattering setup (4). We also present typical results of each setup (formation of amino acids, aldehydes, epoxides; synthesis of hydrogen terminated carbon chains as precursors to complex PAHs and to carbonaceous dust grains in general; nitriles as precursor to amino acids).

Jamieson, C. S.↗
NASA NTRS1988

An atmospheric pressure flow reactor: Gas phase kinetics and mechanism in tropospheric conditions without wall effects

A new type of gas phase flow reactor, designed to permit the study of gas phase reactions near 1 atm of pressure, is described. A general solution to the flow/diffusion/reaction equations describing reactor performance under pseudo-first-order kinetic conditions is presented along with a discussion of critical reactor parameters and reactor limitations. The results of numerical simulations of the reactions of ozone with monomethylhydrazine and hydrazine are discussed, and performance data from a prototype flow reactor are presented.

Koontz, Steven L.↗
NASA NTRS2006

Fluorescence Spectroscopy of Gas-phase Polycyclic Aromatic Hydrocarbons

The purpose of this investigation was to produce fluorescence spectra of polycyclic aromatic hydrocarbon (PAH) molecules in the gas-phase for comparison with blue luminescence (BL) emission observed in astrophysical sources Vijh et al. (2004, 2005a,b). The BL occurs roughly from 350 to 450 nm, with a sharp peak near 380 nm. PAHs with three to four rings, e.g. anthracene and pyrene, were found to produce luminescence in the appropriate spectral region, based on existing studies. Relatively few studies of the gas-phase fluorescence of PAHs exist; those that do exist have dealt primarily with the same samples commonly available for purchase such as pyrene and anthracene. In an attempt to understand the chemistry of the nebular environment we also obtained several nitrogen substituted PAHs from our colleagues at NASA Ames. In order to simulate the astrophysical environment we also took spectra by heating the PAHs in a flame. The flame environment counteracts the formation of eximers and permits the spectroscopy of free-flying neutral molecules. Experiments with coal tar demonstrate that fluorescence spectroscopy reveals primarily the presence of the smallest molecules, which are most abundant and which possess the highest fluorescence efficiencies. One gas-phase PAH that seems to fit the BL spectrum most closely is phenanthridine. In view of the results from the spectroscopy of coal tar, a compound containing a mixture of PAHs ranging from small to very large PAH molecules, we can not preclude the presence of larger PAHs in interstellar sources exhibiting BL.

Thomas, J. D.↗
DOE OSTI2025

CoURAGE Urban Gas-Phase NH3

1-second Picarro gas-phase ammonia (NH3) measurements were collected as part of a 3-month intensive operation period (IOP) from mid-March through mid-June that was funded by the DOE Biological and Environment Research project in conjunction with the DOE ARM CoURAGE deployment to the greater Baltimore region. To complement the NH3 measurements at the Mt. Airy regional background S2 site, the Picarro G2103 NH3 analyzer was deployed at the urban atmospheric chemistry supersite ( 39.32057 N, 76.6246 W) to be able to compare and contrast urban vs regional NH3 and urban vs regional aerosol physicochemical properties.

Aerosol Acidity↗
NASA NTRS1971

Gas-phase basicities of amines.

Relative gas-phase basicities of some aliphatic amines have been determined by ion cyclotron resonance spectroscopy. It is found that increasing alkyl substitution increases basicity if similar substituents are compared, that increases in alkyl group size also increase basicity, and that increasing degree of substitution lowers the N-H bond dissociation energy in ammonium ions. Possible origins of these defects are discussed.

Brauman, J. I.↗
NASA NTRS1986

Fluorometric method for the determination of gas-phase hydrogen peroxide

The fluorometric gas-phase hydrogen peroxide procedure is based on the technique used by Lazrus et. al. for the determination of H2O2 in the liquid phase. The analytical method utilizes the reaction of H2O2 with horseradish peroxidase and p-hydroxphenylacetic acid (POPHA) to form the fluorescent dimer of POPHA. The analytical reaction responds stoichiometrically to both H2O2 and some organic hydroperoxides. To discriminate H2O2 from organic hydroperoxides, catalase is used to preferentially destroy H2O2. Using a dual-channel flow system the H2O2 concentration is determined by difference.

Kok, Gregory L.↗
NASA NTRS1992

Laboratory spectra of gas-phase coronene at elevated temperatures

Gas-phase infrared spectra of coronene from 4000 to 400/cm are presented in emission and absorption at temperatures from 350 to 450 C. Peak positions are compared to KBr pellet data and to a previously published neon matrix-isolated coronene spectrum. Relative feature strengths are analyzed and used to estimate a temperature of interstellar PAHs assuming thermal emission.

Kurtz, J.↗
NASA NTRS1994

Continuous-Flow Gas-Phase Bioreactors

Continuous-flow gas-phase bioreactors proposed for biochemical, food-processing, and related industries. Reactor contains one or more selected enzymes dehydrated or otherwise immobilized on solid carrier. Selected reactant gases fed into reactor, wherein chemical reactions catalyzed by enzyme(s) yield product biochemicals. Concept based on discovery that enzymes not necessarily placed in traditional aqueous environments to function as biocatalysts.

Wise, Donald L.↗
DOE OSTI2021

Gas-phase ion-molecule interactions in a collision reaction cell with triple quadrupole-inductively coupled plasma mass spectrometry: Investigations with N 2 O as the reaction gas

Nitrous oxide (N 2 O) was used as a reaction gas to investigate the gas phase ion-molecule interactions using the Agilent 8900 QQQ-ICP-MS. A multi-element standard containing 45 elements with masses ranging from 9 to 208 u was measured in the presence and absence of N 2 O. The main product ion species observed were oxides and nitrides. Comparison of the N 2 O reaction results with similar measurements conducted with O 2 revealed that N 2 O was more effective at forming oxides in general: the elements Cd and Pb were shown to produce oxides with N 2 O where the reaction did not occur with O 2 . Nitrous oxide was also shown to produce a significant amount of nitride species in a few cases. The general reactivity was shown to be consistent with density functional theory (DFT)-predicted reaction enthalpies, such that all predicted exothermic reactions produced product ions at levels at least 1% of the unreacted ion. Our results show that reaction enthalpy is a reasonable predictor of reactivity with N2O on the timescales of the interactions in non-thermal ICP-MS/MS systems. Our work demonstrates the utility of two relatively new platforms (commercial elemental ICP-MS/MS and EMSL Arrows interface to the NWChem program suite), which allows for the study of a large number of elements within a short period. While DFT with the basis sets utilized here is not the most accurate computational method, it is also not computationally expensive and is shown to be suitable for predicting gas phase reactivity in the QQQ-ICP-MS for the majority of ions studied. Here, the ease and rapidity of data collection and DFT calculations has the potential to be very impactful for the identification of targeted reaction chemistries to be leveraged for analytical method development, such as for the inline separation of isobaric interferences from analytes of interest.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Gas phase protonated nicotine is a mixture of pyridine- and pyrrolidine-protonated conformers: implications for its native structure in the nicotinic acetylcholine receptor

The infrared (IR) spectra of gas phase protonated nicotine has been measured in the never-before probed N–H “fingerprint region” (3200–3500 cm -1 ). The protonated molecules generated by an electrospray source are thermalized in the first ion trap with water vapor and He gas at a pre-determined temperature prior to being probed by IR spectroscopy in the second ion trap at 4 K. The IR spectra exhibit two N–H stretching bands which are assigned to the pyridine and pyrrolidine protomers with the aid of high-level electronic structure calculations. This finding is in sharp contrast to previous spectroscopic studies that suggested a single population of the pyridine protomer. The relative populations of the two protomers vary by changing the temperature of the thermalizing trap from 180-300 K. The relative conformer populations at 240 K and 300 K are well reproduced by the theoretical calculations, unequivocally determining that gas phase nicotine is a 3 : 2 mixture of both pyridine and pyrrolidine protomers at room temperature. The thermalizing anhydrous vapor does not result in any population change. It rather demonstrates the catalytic role of water in achieving equilibrium between the two protomers. The combination of IR spectroscopy and electronic structure calculations establish the small energy difference between the pyridine and pyrrolidine protomers in nicotine. Finally, one of the gas phase nicotine pyrrolidine protomers has the closest conformational resemblance among all low-lying energy isomers with the X-ray structure of nicotine in the nicotinic acetylcholine receptor (nAChR).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Real-Time Measurements of Gas-Phase Medium-Chain Chlorinated Paraffins Reveal Daily Changes in Gas-Particle Partitioning Controlled by Ambient Temperature

Chlorinated paraffins (CPs) are synthetic polychlorinated n-alkanes produced as mixtures of a range of C x Cl y H 2x–y+2 formulas. CPs have numerous industrial applications but are toxic, long-lived, and environmentally ubiquitous with environmental releases occurring throughout their production, use, and disposal. Short-chain chlorinated paraffins (SCCPs, C 10–13 ) have been regulated by the United States Environmental Protection Agency since 2009 and by the Stockholm Convention since 2017. SCCP regulation is expected to cause increased production of medium-chain chlorinated paraffins (MCCPs; C 14–17 ), which are currently under consideration for Stockholm Convention regulations. Thus, there is a need to improve the understanding of MCCP environmental transport, distribution, and fate. Existing measurements are limited in their spatial and temporal coverage. Measurements of CP atmospheric loading are particularly scarce. Historically, these measurements have required long sampling times, obscuring the temporal behavior of atmospheric CPs. We report real-time in situ measurements of 18 gas-phase MCCPs. These measurements were made in the United States Southern Great Plains with nitrate ion chemical ionization mass spectrometry (NO 3 –CIMS). Here, the estimated average lower-limit concentration of MCCPs is on the order of single-digit ng/m 3 . MCCP diel behavior is partially explained by gas-particle partitioning with implications for MCCP transport and lifetimes.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2026

Electron-Deficient Phenazines: Synthesis, Structures, Redox, and Optoelectronic Properties in the Gas Phase, in Solution, and in the Solid State

High-temperature gas-phase reactions of 1,4-C4F8I2 with phenazine (PHNZ) afforded new thermally- and air-stable derivatives with cyclo-C4F8 substituents, viz. 1,2-PHNZ(C4F8), 2,3-PHNZ(C4F8), 1,2:6,7-PHNZ(C4F8)2, 1,2:7,8-PHNZ(C4F8)2, and 1,2:8,9-PHNZ(C4F8)2. Reactions in the presence of Cu powder resulted in reductive-defluorination/aromatization of some of the cyclo-C4F8 substituents to produce 2,3-PHNZ(C4F4), 2,3-PHNZ(C4HF3), and 1,2:6,7-PHNZ(C4F8)(C4F4), which are formally tri- or tetrafluoro derivatives of benzo[a]phenazine. Single-crystal X-ray diffraction structures of these compounds demonstrate the planarity of 2,3-PHNZ(C4F4) and 2,3-PHNZ(C4HF3) and ordered p-stacking in 1,2-PHNZ(C4HF3), 1,2-PHNZ(C4F4), 1,2-PHNZ(C4F8), and 2,3-PHNZ(C4F8). Low-temperature gas-phase photoelectron spectra of the PHNZ(C4F8)1,2 compounds show that they are strong electron acceptors, with the three PHNZ(C4F8)2 isomers having electron affinities exceeding that of C60. Cyclic voltammetry in acetonitrile show that the five PHNZ(C4F8)1,2 compounds exhibit reversible one-electron reductions with large positive shifts in their reduction potentials relative to unsubstituted PHNZ. Spectroelectrochemical absorption and EPR spectra of PHNZ(C4F8)1,2- • anion radicals and extensive DFT calculations revealed the significant role that the different substitution patterns have on determining the optoelectronic properties of the PHNZ(C4F8)1,2 derivatives and PHNZ(C4F8)1,2- • anion radicals. Time-resolved microwave conductivity measurements and photoluminescence spectra of blends of the PHNZ(C4F8)1,2 derivatives with the donor poly(3-hexylthiophene) (P3HT) were recorded to assess the possible use of the new compounds in optoelectronic devices.

Balser, Sebastian↗