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At least 973 records · Page 54
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

The H•/H– Redox Couple and Absolute Hydration Energy of H–

A supermolecule-continuum approach with water clusters up to n = 16 H2O molecules has been used to predict the absolute hydration free energies at 298 K ($\Delta$G hyd ) of both hydrogen (H•) and hydride (H - ) to be 4.6 and -78 ± 2 kcal/mol, respectively. These values are combined with a high accuracy prediction of the gas phase electron affinity ($\Delta$G gas,298K = -16.9 kcal/mol) to determine the aqueous electron affinity of H• of 99.5 ± 2 kcal/mol, which yields a reduction potential for H• vs SHE of -0.03 ± 0.15 V. This value is in agreement within 0.2 V with most estimates obtained using a wide variety of approaches. The results of this study can be used to improve the absolute hydricity scale in water which provides additional insights into how a putative hydride interacts with solvent, but do not change the ability to predict the relative reactivity of two species using relative hydricity scales.

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

SDSS-IV MaNGA: the physical origin of off-galaxy H α blobs in the local Universe

ABSTRACT H α blobs are off-galaxy emission-line regions with weak or no optical counterparts. They are mostly visible in H α line, appearing as concentrated blobs. Such unusual objects have been rarely observed and studied, and their physical origin is still unclear. We have identified 13 H α blobs in the public data of MaNGA survey, by visually inspecting both the optical images and the spatially resolved maps of H α line for ∼4600 galaxy systems. Among the 13 H α blobs, 2 were reported in previously MaNGA-based studies and 11 are newly discovered. This sample, though still small in size, is by far the largest sample with both deep imaging and integral field spectroscopy. Therefore, for the first time we are able to perform statistical studies to investigate the physical origin of H α blobs. We examine the physical properties of these H α blobs and their associated galaxies, including their morphology, environments, gas-phase metallicities, kinematics of ionized gas, and ionizing sources. We find that the H α blobs in our sample can be broadly divided into two groups. One is associated with interacting/merging galaxy systems, of which the ionization is dominated by shocks or diffuse ionized gas. It is likely that these H α blobs used to be part of their nearby galaxies, but were stripped away at some point due to tidal interactions. The other group is found in gas-rich systems, appearing as low-metallicity star-forming regions that are visually detached from the main galaxy. These H α blobs could be associated with faint discs, spiral arms, or dwarf galaxies.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1988

Direct mass spectrometric identification of silicon oxychloride compounds

Silicon oxychloride compounds formed during the high temperature reaction of Si and SiC with Cl2/O2 mixtures at 930 and 950 C have been directly observed with an atmospheric pressure mass spectrometer sampling system. Molecules with the formulas Si2OCl6 and Si3OCl8 have been identified. These compounds are very likely formed by a gas phase reaction between the oxygen gas in the system and silicon tetrachloride which is produced by chlorination of the silicon-based material.

Marra, John E.↗
NASA NTRS2004

Nitric Acid Uptake on Subtropical Cirrus Cloud Particles

The redistribution of HNO3 via uptake and sedimentation by cirrus cloud particles is considered an important term in the upper tropospheric budget of reactive nitrogen. Numerous cirrus cloud encounters by the NASA WB-57F high-altitude research aircraft during CRYSTAL-FACE were accompanied by the observation of condensed-phase HNO3 with the NOAA chemical ionization mass spectrometer. The instrument measures HNO3 with two independent channels of detection connected to separate forward- and downward-facing inlets that allow a determination of the amount of HNO3 condensed on ice particles. Subtropical cirrus clouds, as indicated by the presence of ice particles, were observed coincident with condensed-phase HNO3 at temperatures of 197 K - 224 K and pressures of 122 hPa - 224 hPa. Maximum levels of condensed-phase HNO3 approached the gas-phase equivalent of 0.8 ppbv. Ice particle surface coverages as high as 1.4- 10(exp 14) molecules/sq cm were observed. A dissociative Langmuir adsorption model, when using an empirically derived HNO3 adsorption enthalpy of -11.0 kcal/mol, effectively describes the observed molecular coverages to within a factor of 5. The percentage of total HNO3 in the condensed phase ranged from near zero to 100% in the observed cirrus clouds. With volume-weighted mean particle diameters up to 700 pm and particle fall velocities up to 10 m/s, some observed clouds have significant potential to redistribute HNO3 in the upper troposphere.

Source record↗
NASA NTRS2004

Nitric Acid Uptake on Subtropical Cirrus Cloud Particles

The redistribution of HNO3 via uptake and sedimentation by cirrus cloud particles is considered an important term in the upper tropospheric budget of reactive nitrogen. Numerous cirrus cloud encounters by the NASA WB-57F high-altitude research aircraft during the Cirrus Regional Study of Tropical Anvils and Cirrus Layers-Florida Area Cirrus Experiment (CRYSTAL-FACE) were accompanied by the observation of condensed-phase HNO3 with the NOAA chemical ionization mass spectrometer. The instrument measures HNO3 with two independent channels of detection connected to separate forward and downward facing inlets that allow a determination of the amount of HNO3 condensed on ice particles. Subtropical cirrus clouds, as indicated by the presence of ice particles, were observed coincident with condensed-phase HNO3 at temperatures of 197-224 K and pressures of 122-224 hPa. Maximum levels of condensed-phase HNO3 approached the gas-phase equivalent of 0.8 ppbv. Ice particle surface coverages as high as 1.4 # 10(exp 14) molecules/ square cm were observed. A dissociative Langmuir adsorption model, when using an empirically derived HNO3 adsorption enthalpy of -11.0 kcal/mol, effectively describes the observed molecular coverages to within a factor of 5. The percentage of total HNO3 in the condensed phase ranged from near zero to 100% in the observed cirrus clouds. With volume-weighted mean particle diameters up to 700 ?m and particle fall velocities up to 10 m/s, some observed clouds have significant potential to redistribute HNO3 in the upper troposphere.

Popp, P. J.↗
NASA NTRS2011

The C-12/C-13 Ratio as a Chemistry Indicator

Isotopic ratios of elements are considered powerful tools, e.g. in tracing the origin of solar system body materials, or the degree of nucleosynthesis processing throughout the Galaxy. In interstellar molecules, some isotopic ratios like H/D and C-12/C-13 can also be used as indicators of their chemical origin. Isotope fractionation in gas-phase chemical reactions and gas-dust interaction makes observations of the ratio between C-12 and C-13 isotopologues suitable to distinguish between different formation scenarios. We will present observations of the C-12/C-13 ratio in methanol and formaldehyde towards a sample of embedded, massive young stellar objects. In relation to this we also present results from theoretical modeling showing the usefulness of the C-12/C-13 ratio as a chemistry indicator.

Wirstroem, Eva↗
DOE OSTI2022

Coupled Interfacial and Bulk Kinetics Govern the Timescales of Multiphase Ozonolysis Reactions

Chemical transformations in aerosols impact the lifetime of particle phase species, the fate of atmospheric pollutants, and both climate- and health-relevant aerosol properties. Timescales for multiphase reactions of ozone in atmospheric aqueous phases are governed by coupled kinetic processes between the gas phase, the particle interface, and its bulk, which respond dynamically to reactive consumption of O 3 . However, models of atmospheric aerosol reactivity often do not account for the coupled nature of multiphase processes. Herein, to examine these dynamics, we use new and prior experimental observations of aqueous droplet reaction kinetics, including three systems with a range of surface affinities and ozonolysis rate coefficients ( trans -aconitic acid (C 6 H 6 O 6 ), maleic acid (C 4 H 4 O 4 ), and sodium nitrite (NaNO 2 )). Using literature rate coefficients and thermodynamic properties, we constrain a simple two-compartment stochastic kinetic model which resolves the interface from the particle bulk and represents O 3 partitioning, diffusion, and reaction as a coupled kinetic system. Our kinetic model accurately predicts decay kinetics across all three systems, demonstrating that both the thermodynamic properties of O 3 and the coupled kinetic and diffusion processes are key to making accurate predictions. An enhanced concentration of adsorbed O 3 , compared to gas and bulk phases is rapidly maintained and remains constant even as O 3 is consumed by reaction. Multiphase systems dynamically seek to achieve equilibrium in response to reactive O 3 loss, but this is hampered at solute concentrations relevant to aqueous aerosol by the rate of O 3 arrival in the bulk by diffusion. As a result, bulk-phase O 3 becomes depleted from its Henry's law solubility. This bulk-phase O 3 depletion limits reaction timescales for relatively slow-reacting organic solutes with low interfacial affinity (i.e., trans-aconitic and maleic acids, with k rxn ≈ 10 3 -10 4 M -1 s -1 ), which is in contrast to fast-reacting solutes with higher surface affinity (i.e., nitrite, with k rxn ≈ 10 5 M -1 s -1 ) where surface reactions strongly impact the observed decay kinetics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Untapped Benefits of Porous Liquids for Gas Capture: Low-Energy Regeneration

Current liquid-phase gas capture materials incur high operational costs due to energy-intensive regeneration processes, creating an industrial need for alternative materials that retain engineering benefits while reducing energy requirements. Porous liquids (PLs), liquid-phase materials with permanent internal porosity, have emerged as promising replacements with excellent gas absorption capacity and selectivity. Despite these benefits, evaluation of regeneration in PLs remains rare. In this Perspective, we evaluate the effects of solvent interactions, mass transport, and binding site formation that control PL regeneration. While conventional regeneration methods exist in PLs, the diversity of PL compositions allows for novel regeneration processes including light irradiation via use of photosensitive azobenzene-based cages, isostatic compression to collapse internal pore structures, and localized heating via sonication for gas desorption. In conclusion, the wide variability in porous host materials that generate the internal porosity in PLs facilitates innovative low-energy regeneration pathways, positioning them as a transformative solution in separation technologies.

gas capture↗
NASA NTRS1994

The interstellar medium in the starburst regions of NGC 253 and NGC 3256

We discuss observations of the (C II) 158 micrometers, (O I) 63 micrometers, (Si II) 35 micrometers, (O III) 52,88 micrometers, and (S III) 33 micrometers fine-structure transitions toward the central 45 seconds of the starburst galaxies NGC 253 and NGC 3256. The (C II) and (O I) emission probably originates in photodissociated gas at the surfaces of molecular clouds, although a small (less than or approximately 30%) contribution to the (C II) flux from H II regions cannot be ruled out. The (O III) and (S III) lines originate in H II regions and the (Si II) flux is best explained as originating in H II regions with some contribution from photodissociation regions (PDRs). The gas phase silicon abundance is nearly solar in NGC 253, which we interpret as evidence for grain destruction in the starburst region. We find that the photodissociated atomic gas has densities approximately 10(exp 4)/cu cm and temperature 200-300 K. About 2% of the gas is in this phase. The thermal gas pressure in the PDRs, P(PDR)/k approximately 1-3 x 10(exp 6) K/cu cm, might represent the 'typical' interstellar gas pressure in starburst systems. The Far Ultraviolet (FUV) radiation fields illuminating the clouds are 10(exp 3)-10(exp 4) stronger than the local Galactic FUV field and come from the contribution of many closely packed O and B stars. For the central 250 pc of NGC 253, we find that the H II gas has an average density n(sub e) is approximately 400/cu cm. This corresponds to a thermal pressure P(H II)/k approximately 7 x 10(exp 6) K/cu cm which is approximately P(PDR)/k, suggesting that the ionized gas is in pressure equilibrium with the photodissociated gas at the surfaces of molecular clouds. The H II gas fills a significant fraction, approximately 0.01-0.3, of the volume between the clouds. The effective temperature of the ionizing stars in NGC 253 is greater than or approximately 34,500 K; 2 x 10(exp 5) O7.5 stars would produce the observed Lyman countinuum photon luminosity. The average separation between the stars is approximately 3 pc. Applying the simple model for the interstellar medium in galactic nuclei of Wolfire, Tielens, & Hollenbach (1990), we find the molecular gas in the central regions of NGC 253 and NGC 3256 to be distributed in a large number (5 x 10(exp 3) to 5 x 10(exp 5)) of small (0.5-2 pc), dense (approximately 10(exp 4)/cu cm) clouds (or alternatively 'thin-flattened' structures) with volume filling factors 10(exp -3) to 10(exp -2), very different from the local Interstellar Medium (ISM) of the Galaxy. We suggest a self-consistent scenario for the ISM in NGC 253 in which clouds and H II gas are in pressure balance with a supernova-shocked, hot 1-3 x 10(exp 6) K, low-density (approximately 10(exp 4)/cu cm), all pervasive medium. A feedback mechanism may be indicated in which the pressure generated by the supernovae compresses the molecular clouds and triggers further massive star formation. The similarity of ISM parameters deduced for NGC 253, NGC 3256, and M82 (Lord et al. 1993) suggests that the ISM properties are independent of the luminosity of the starburst or the triggering mechanism, but are rather endemic to starburst systems. The starburst in NGC 3256 appears to be a scaled-up version of the NGC 253 and M82 starbursts.

Carral, P.↗
DOE OSTI2020

Tuning Internal Strain in Metal–Organic Frameworks via Vapor Phase Infiltration for CO 2 Reduction

Abstract A gas‐phase approach to form Zn coordination sites on metal–organic frameworks (MOFs) by vapor‐phase infiltration (VPI) was developed. Compared to Zn sites synthesized by the solution‐phase method, VPI samples revealed approximately 2.8 % internal strain. Faradaic efficiency towards conversion of CO 2 to CO was enhanced by up to a factor of four, and the initial potential was positively shifted by 200–300 mV. Using element‐specific X‐ray absorption spectroscopy, the local coordination environment of the Zn center was determined to have square‐pyramidal geometry with four Zn−N bonds in the equatorial plane and one Zn‐OH 2 bond in the axial plane. The fine‐tuned internal strain was further supported by monitoring changes in XRD and UV/Visible absorption spectra across a range of infiltration cycles. The ability to use internal strain to increase catalytic activity of MOFs suggests that applying this strategy will enhance intrinsic catalytic capabilities of a variety of porous materials.

Yang, Fan↗
DOE OSTI2023

2023 American Society for Mass Spectrometry (ASMS) 71st Annual Conference on Mass Spectrometry and Allied Topics

Introduction (120 words max) Understanding metal-cluster chemistry occuring at solvent boundaries in the aqueous and organic phases has applications in environments from cellular processes to nuclear fuel reprocessing. Transport of metal ions at the boundaries from aqueous to organic phases involves forming a metal-ligand complex, and wherever the initial metal coordination environment is significantly different from the final one, the metal transitions through a series of transient species in passing from one phase to another. Here an investigation of the role of coordination in the chemistry of the transient species using gas-phase measurements that are free of solvent effects to better understand the binding of complexes of metals with triphenylphosphine chalcogenide ligands, examining metal-ligand homo- and hetero-dimers to better understand transient species. Methods (120 word max) Mass spectrometry and collision induced dissociation (CID) experiments were performed with a Bruker (Billerica, MA, USA) micrOTOF-Q II quadrupole time-of-flight mass spectrometer (QTOF) and Bruker amaZon speed ETD (ion trap). High resolution/high mass accuracy spectra were generated using the QTOF. External calibration was performed with Agilent (Santa Clara, CA, USA) ESI-L Low Concentration tuning mix. Both mass spectrometers were equipped with either the electrospray ionization source or nanospray sources. Metal samples were prepared between 40 – 60 uM of the metal-ligand complex in 25% water and 75% acetonitrile. Metal-ion clusters were isolated and subjected to collision induced dissociation. Density functional theory calculations were performed. Preliminary Data or Plenary Speakers Abstract (300 words max) Metal ion clusters with triphenylphosphine chalcogenide ligands were observed for group I metals with triphenylphosphine chalcogenide samples in the mass spectrum upon electrospray ionization. For each metal ligand complex of interest, the parent ion was isolated and collision induced dissociation fragmentation spectra were acquired. We observed clusters of group I metal with triphenylphosphine oxide, triphenyl phosphine sulfide, and triphenylphosphine selenide, with homodimers and heterodimer formation. In samples where the ligands were mixed, we observed mixed sodium ligand clusters at varying amounts. These mixed ligand clusters were fragmented. Metal clusters of mixed ligand dimers containing triphenylphosphine oxide showed preferential loss of the other ligand, either triphenylphosphine sulfide or triphenyl selenide. In samples with mixed triphenylphosphine sulfide and triphenylphosphine selenium ligands, sodium bound similarly between the ligands, and losses were more evenly split, showing loss ratio upon CID with losses of triphenylphosphine sulfide:triphenylphosphine selenide 43:57 ratio observed on CID. These results suggest that the oxide binds significantly more strongly than either the selenium or sulfur triphenylphosphine ligand, and the sulfur and selenium ligands are more evenly bound. Calculations were performed using density functional theory to calculate likely structures and bond energies between the group I metal and the ligands. Novel Aspect Novel analysis of sodium bound dimers with chalcogenide triphenylphosphine ligands were investigated using mass spectrometry and theoretical calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Sustainable H 2 -Rich Syngas Production via Microwave-Assisted vs Conventional Catalysis of Pinewood

Catalytic gasification of biomass is a promising method for producing hydrogen-rich syngas, which is a valuable resource for cleanenergy applications. In this study, microwave-assisted biomass gasification was compared with conventional thermally driven biomass gasification using pinewood as the biomass without the use of external gasifying agents (such as air, steam, and CO 2 ), under non-catalytic and catalytic conditions. The catalysts consisted of either an iron or a nickel catalyst, and the pinewood used as biomass contained 42% oxygen. This comparative analysis explores the differences in reaction chemistry, product yields, and the role of key reactions such as the water gas shift (WGS) reaction, Boudouard reaction, etc. The gas-phase and liquid-phase products were analyzed using online gas chromatography, and the fresh and spent catalysts were analyzed using X-ray diffraction (XRD) techniques. It was found that microwave-assisted gasification offers advantages in terms of enhanced reaction efficiency, catalyst stability, and hydrogen yield. For the microwave-assisted reaction, the gas yield reached 87%, the char yield was 12.1%, and the tar yield was less than 1% (0.793%) at 550 °C. In contrast, thermal-assisted gasification using the same catalyst produced a gas yield of 85.796%, char yield of 11.438%, and higher tar yield of 2.8% at 900 °C. The higher microwave-assisted performance was attributed to faster heating and better control over reaction conditions, higher reaction rates, and more favorable conditions for hydrogen production.

biomass↗
DOE OSTI2021

Computational thermodynamic study of SiC chemical vapor deposition from MTS-H 2

This study focuses on the computational thermodynamic analysis of the chemical vapor deposition (CVD) of SiC from the methyltrichlorosilane-hydrogen (MTS-H 2 ) using up-to-date thermodynamic databases. High-resolution computation has been performed with the fine intervals of temperature and pressure at the various H 2 /MTS ratios of interest to systematically investigate the deposition condition range (800 to 1600°C, 0 to 26 664 Pa, and H 2 /MTS ratios of 0.1 to 100) to guide experimental exploration. The influence of deposition parameters on the compositions and phase stabilities of the deposit and gas phase pertinent to vapor processing is elucidated. Low pressure and medium temperatures (1000 to 1400°C) are beneficial to reaching a higher SiC deposition efficiency and provide an optimal window for preparing a high-purity (>99 wt.% SiC) deposit. This optimal processing window expands significantly with an increasing H 2 /MTS ratio (<20). These results are supported by a number of previous theoretical and experimental observations. The mass fraction of SiC in deposit is proposed as an additional perspective to understand the discrepancy between thermodynamic calculation and experimental observation of pure CVD SiC at low H 2 /MTS ratios.

36 MATERIALS SCIENCE↗
NASA NTRS1994

Modulations of stratospheric ozone by volcanic eruptions

We have used a time series of aerosol surface based on the measurements of Hofmann to investigate the modulation of total column ozone caused by the perturbation to gas phase chemistry by the reaction N2O5(gas) + H2O(aero) yields 2HNO3(gas) on the surface of stratospheric aerosols. We have tested a range of values for its reaction probability, gamma = 0.02, 0.13, and 0.26 which we compared to unperturbed homogeneous chemistry. Our analysis spans a period from Jan. 1974 to Oct. 1994. The results suggest that if lower values of gamma are the norm then we would expect larger ozone losses for highly enhanced aerosol content that for larger values of gamma. The ozone layer is more sensitive to the magnitude of the reaction probability under background conditions than during volcanically active periods. For most conditions, the conversion of NO2 to HNO3 is saturated for reaction probability in the range of laboratory measurements, but is only absolutely saturated following major volcanic eruptions when the heterogeneous loss dominates the losses of N2O5. The ozone loss due to this heterogeneous reaction increases with the increasing chlorine load. Total ozone losses calculated are comparable to ozone losses reported from TOMS and Dobson data.

Blanchette, Christian↗