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At least 199 records · Page 11

Modeling Aerosol Nucleation

The goal of this work has been to understand how nitric acid condenses on cirrus ice cloud particles by analyzing data obtained during the SAGE III Ozone Loss and Validation Experiment (SOLVE) research mission based out of Kiruna, Sweden. Ms. Gamblin simultaneously analyzed gas phase nitric acid data along with particulate NO, data, particulate, vapor and gas-phase water data from several different instruments, particle size data, which included surface area and volume measurements, ozone concentration data as well as temperature, pressure and GPS coordinates of the sampled air parcel. All parameters where held constant with only one allowed to vary in order to determine what controls the extent to which nitric acid will condensation on ice. In addition, this data was compared to theoretical values of nitric acid condensation on ice based upon recent laboratory data. Comparison of these two data sets shows the field data does not agree with what is expected in the laboratory at comparable temperatures and nitric acid pressures. The most significant difference is that surface coverages in the atmosphere were found to be elevated relative to surface coverages measured in the laboratory. The results of this study were accepted for publication by Geophysical Research Letters.

Toon, Owen B.↗

Radioactive Waste Sludge Washing and Demonstration of the Nitric-Glycolic Acid Flowsheet for Sludge Batch 10 Qualification

For each sludge batch that is processed in the Defense Waste Processing Facility (DWPF), the Savannah River National Laboratory (SRNL) performs qualification testing to demonstrate that the sludge batch (SB) is processible. During processing of SB9, DWPF will be transitioning from the Nitric-Formic Acid (NFA) flowsheet to the Nitric-Glycolic Acid (NGA) flowsheet. Thus, the qualification of SB10 was requested to only be performed using the NGA flowsheet. In order to qualify the batch for the NGA flowsheet, Sludge Receipt and Adjustment Tank (SRAT) and Slurry Mix Evaporator (SME) cycles, designated SC-19, were performed using SB10 Tank 51 sample material. SRNL received Tank 51 material in the midst of Tank Farm washing. SRNL continued the washing in the SRNL Shielded Cells. The SRNL process included the addition of Sodium Reactor Experiment (SRE) material from H Canyon, simulating the transfer of SRE from H Canyon to Tank 51 during Tank Farm washing. The washed SB10 Tank 51 material, with SRE, was characterized prior to flowsheet qualification testing.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Elucidation of odd-chain dicarboxylate metabolism in Acinetobacter baylyi and application to polyethylene upcycling

Polyethylene (PE) is a versatile polymer, but its end-of-life management is challenging due to its recalcitrant structure. We present a promising approach combining chemical degradation and bio-upcycling to convert postconsumer PE waste into a value-added bioproduct. Specifically, PE was degraded into acetic acid and C 4 –C 7 dicarboxylic acids by nitric acid. We then elucidated the catabolic pathways for glutarate (C 5 ) and pimelate (C 7 ) in the nonmodel bacterium Acinetobacter baylyi ADP1 through RNA sequencing, phenotyping, and enzymatic assays. Whole-genome sequencing of evolved isolates also identified a crucial IclR family transcriptional regulator, DcaS, which acts as a repressor of dicarboxylate metabolism. The reverse-engineered strain exhibited enhanced substrate utilization compared to the wild-type strain. Using rational metabolic engineering, the PE deconstruction products were bioconverted into the valuable chemical lycopene, highlighting the potential of this microbial chassis to produce value-added bioproducts from postconsumer PE waste, thus promoting a circular economy for plastics.

metabolic engineering↗

The Coordination Chemistry and Stoichiometry of Extracted Diglycolamide Complexes of Lanthanides in Extraction Chromatography Materials

Industrial rare earth element (REE) separations predominantly utilize solvent extraction processes tailored toward conventional resources such as bastnäsite, monazite, and ion adsorption clays. Advances in diglycolamide (DGA) chemistry have shown effective extraction characteristics for REE separations. However, limitations associated with traditional DGA solvent extraction techniques, such as third-phase formation and gelling, have hindered commercial viability. By supporting DGA extractants on porous resins such as polystyrene divinyl benzene (PS-DVB), the desirable combination of solvent extraction selectivity and ease of operation of sorbent columns can be achieved. To design a low-cost model for such solid-supported DGAs, extraction characteristics as influenced by the underlying coordination chemistry must be explored to achieve efficient functional systems. Within this study, we report novel DGA resin materials, each incorporating one of the DGAs N,N,N’,N’-tetra-(1-octyl)-3-oxapentane-1,5-diamide (TODGA), N,N'-dimethyl-N,N'-dioctyl-3-oxapentane-1,5-diamide (DMDODGA), and 2,2'-oxybis(1-(3-(((2-ethylhexyl)thio)methyl)-4-methylpyrrolidin-1-yl)ethan-1-one) (DEHPDGA). The affinity of DGAs across the lanthanide (Ln) series was evaluated for both hydrochloric acid and nitric acid media with varying Ln feed concentrations to study distribution ratios and loading characteristics. Focusing on dysprosium, extended X-Ray Absorption Fine Structure (EXAFS) and density functional theory (DFT) calculations were also utilized to explore coordination chemistry and their effects on ligand performance. The general trend for both acid media resulted in DMDODGA having the highest extraction strength of all three DGAs at varying acid concentrations. Coordination-chemistry analysis supported by loading data, DFT calculations, and EXAFS results under forced loading conditions posited less than the expected 3:1 ligand-to-metal coordination.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Online characterization of primary and secondary emissions of particulate matter and acidic molecules from a modern fleet of city buses

The potential impact of transitioning from conventional fossil fuel to a non-fossil-fuel vehicle fleet was investigated by measuring primary emissions via extractive sampling of bus plumes and assessing secondary mass formation using the Gothenburg Potential Aerosol Mass (Go:PAM) reactor from 76 in-use transit buses. Online chemical characterization of gaseous and particulate emissions from these buses was conducted using chemical ionization mass spectrometry (CIMS) with acetate as the reagent ion, coupled with the Filter Inlet for Gases and AEROsols (FIGAERO). Acetate reagent ion chemistry selectively ionizes acidic compounds, including organic and inorganic acids, as well as nitrated and sulfated organics. A significant reduction (48 %–98 %) in fresh particle emissions was observed in buses utilizing compressed natural gas (CNG), biodiesels like rapeseed methyl ester (RME) and hydrotreated vegetable oil (HVO), and hybrid-electric HVO (HVO HEV ) compared to diesel (DSL). However, secondary particle formation from photooxidation of emissions was substantial across all the fuel types. The median ratio of particle mass emission factors of aged to fresh emissions increased in the following order: DSL buses at 4.0, HVO buses at 6.7, HVO HEV buses at 10.5, RME buses at 10.8, and CNG buses at 84. Of the compounds that can be identified by CIMS, fresh gaseous emissions from all Euro V/EEV (Enhanced Environmentally friendly Vehicle) buses, regardless of fuel type, were dominated by nitrogen-containing compounds such as nitrous acid (HONO), nitric acid (HNO 3 ), and isocyanic acid (HNCO), alongside small monoacids (C 1 –C 3 ). Notably, the emission of nitrogen-containing compounds was lower in Euro VI buses equipped with more advanced emission control technologies. Secondary gaseous organic acids correlated strongly with gaseous HNO 3 signals (R 2 =0.85–0.99) in Go:PAM, but their moderate to weak correlations with post-photooxidation secondary particle mass suggest that they are not reliable tracers of secondary organic aerosol formation from bus exhaust. Our study highlights that non-regulated compounds and secondary pollutant formation, not currently addressed in legislation, are crucial considerations in the evaluation of environmental impacts of future fuel and engine technology shifts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Simulations of aerosol pH in China using WRF-Chem (v4.0): sensitivities of aerosol pH and its temporal variations during haze episodes

Aerosol pH is a fundamental property of aerosols in terms of atmospheric chemistry and its impact on air quality, climate, and health. Precise estimation of aerosol pH in chemical transport models (CTMs) is critical for aerosol modeling and thus influences policy development that partially relies on results from model simulations. We report the Weather Research and Forecasting Model coupled with Chemistry (WRF-Chem) simulated PM 2.5 pH over China during a period with heavy haze episodes in Beijing, and explore the sensitivity of the modeled aerosol pH to factors including emissions of nonvolatile cations (NVCs) and NH 3 , aerosol phase state assumption, and heterogeneous production of sulfate. We find that default WRF-Chem could predict spatial patterns of PM 2.5 pH over China similar to other CTMs, but with generally lower pH values, largely due to the underestimation of alkaline species (NVCs and NH 3 ) and the difference in thermodynamic treatments between different models. Increasing NH 3 emissions in the model would improve the modeled pH in comparison with offline thermodynamic model calculations of pH constrained by observations. In addition, we find that the aerosol phase state assumption and heterogeneous sulfate production are important in aerosol pH predictions for regions with low relative humidity (RH) and high anthropogenic SO 2 emissions, respectively. These factors should be better constrained in model simulations of aerosol pH in the future. Analysis of the modeled temporal trend of PM 2.5 pH in Beijing over a haze episode reveals a clear decrease in pH from 5.2 ± 0.9 in a clean period to 3.6 ± 0.5 in a heavily polluted period. The increased acidity under more polluted conditions is largely due to the formation and accumulation of secondary species including sulfuric acid and nitric acid, even though being modified by alkaline species (NVCs, NH 3 ). Our result suggests that NO 2 oxidation is unlikely to be important for heterogeneous sulfate production during the Beijing haze as the effective pH for NO 2 oxidation of S(IV) is at a higher pH of ~6.

54 ENVIRONMENTAL SCIENCES↗

Ambient cure polyimide foams

Flame and temperature resistant polyimide foams are prepared by the reaction of an aromatic dianhydride, (pyromellitic dianhydride) with an aromatic polyisocyanate, (polymethylene polyphenylisocyanate), in the presence of an inorganic acid and furfuryl alcohol. Usable acids include dilute sulfuric acid, dilute nitric acid, hydrochloric acid, polyphosphoric acid, and phosphoric acid, with the latter being preferred. The dianhydride and the isocyanate in about equimolar proportions constitute about 50% of the reaction mixture, the rest being made up with the acid and the alcohol in a ratio of about 1:10. An exothermic reaction between the acid and the alcohol provides the heat necessary for the other components to polymerize without recourse to external heat sources. The mixture can be sprayed on any surface to form polymeric foam in locations where the application of heat is not practical or possible, for instance, between walls or on mine tunnel surfaces.

Sawko, P. M.↗

Satellite observations of upper atmosphere O3 and HNO3 from the Limb Infrared Monitor of the Stratosphere /LIMS/ experiment on Nimbus 7

The Limb Infrared Monitor of the Stratosphere (LIMS) experiment, launched on-board the Nimbus satellite, was designed to measure both day and night limb radiance which is used to infer upper atmosphere temperature profiles and chemical compound concentrations important in the study of ozone chemistry. The LIMS instrument is a six channel, limb scanning, thermal radiometer which uses HgCdTe detectors, cooled to approximately 64 K. Measurements include ozone, water vapor, nitrogen dioxide, and nitric acid. The ozone and nitric acid channels are centered at approximately 9.6 microns and 11.3 microns, respectively. Results from the channels are described with an emphasis on data validation. The O3 and HNO3 channels have demonstrated high measurement precision.

Russell, J. M., III↗

Observed particle evolution in the polar stratospheric cloud of January 24, 1989

Particle-size distributions measured from the NASA ER-2 with the new Forward Scattering Spectrometer Probe 300 in a type I polar stratospheric cloud (PSC) on January 24, 1989 show a volume mode near 0.8 micron in diameter. The large increase in particle concentration and volume after cloud entry did not occur until the apparent saturation ratio of nitric acid with respect to nitric acid trihydrate reached 10, but at ratios near 1 subtle changes in the size distribution suggest some type I particles were present. Particle concentrations in cloud of 15-17/cu cm were greater than the CN concentrations of 5-7/cu cm just outside of cloud, suggesting nucleation on more than just sulfate particles. Some particles greater than 4 microns in diameter were observed in a region which was saturated with respect to ice.

Dye, J. E.↗

An experimental study of growth and phase change of polar stratospheric cloud particles

This report describes the progress made on understanding phase changes related to solutions which may comprise Polar Stratospheric Clouds. In particular, it is concerned with techniques for investigating specific classes of metastability and phase change which may be important not only in Polar Stratospheric Clouds but in all atmospheric aerosols in general. While the lower level atmospheric aerosol consists of mixtures of (NH4)(SO4)2, NH4HSO4, NaCl among others, there is evidence that aerosol at PSC levels is composed of acid aerosol, either injected from volcanic events (such as Pinatubo) or having diffused upward from the lower atmosphere. In particular, sulfuric acid and nitric acid are known to occur at PSC levels, and are suspected of catalyzing ozone destruction reactions by adsorption on surfaces of crystallized particles. The present study has centered on two approaches: (1) the extent of supercooling (with respect to ice) and supersaturation (with respect to hydrate) and the nature of crystal growth in acid solutions of specific molality; and (2) the nature of growth from the vapor of HNO3 - H2O crystals both on a substrate and on a pre-existing aerosol.

Hallett, John↗

A Laboratory Study on the Phase Transition for Polar Stratospheric Cloud Particles

The nucleation and growth of different phases of simulated polar stratospheric cloud (PSC) particles were investigated in the laboratory. Solutions and mixtures of solutions at concentrations 1 to 5 m (molality) of ammonium sulfate, ammonium bisulfate, sodium chloride, sulfuric acid, and nitric acid were supercooled to prescribed temperatures below their equilibrium melting point. These solutions were contained in small diameter glass tubing of volumes ranging from 2.6 to 0.04 ml. Samples were nucleated by insertion of an ice crystal, or in some cases by a liquid nitrogen cooled wire. Crystallization velocities were determined by timing the crystal growth front passages along the glass tubing. Solution mixtures containing aircraft exhaust (soot) were also examined. Crystallization rates increased as deltaT2, where deltaT is the supercooling for weak solutions (2 m or less). The higher concentrated solutions (greater than 3 m) showed rates significantly less than deltaT2. This reduced rate suggested an onset of a glass phase. Results were applied to the nucleation of highly concentrated solutions at various stages of polar stratospheric cloud development within the polar stratosphere.

Teets, Edward H., Jr.↗

Homogenous Surface Nucleation of Solid Polar Stratospheric Cloud Particles

A general surface nucleation rate theory is presented for the homogeneous freezing of crystalline germs on the surfaces of aqueous particles. While nucleation rates in a standard classical homogeneous freezing rate theory scale with volume, the rates in a surface-based theory scale with surface area. The theory is used to convert volume-based information on laboratory freezing rates (in units of cu cm, seconds) of nitric acid trihydrate (NAT) and nitric acid dihydrate (NAD) aerosols into surface-based values (in units of sq cm, seconds). We show that a surface-based model is capable of reproducing measured nucleation rates of NAT and NAD aerosols from concentrated aqueous HNO3 solutions in the temperature range of 165 to 205 K. Laboratory measured nucleation rates are used to derive free energies for NAT and NAD germ formation in the stratosphere. NAD germ free energies range from about 23 to 26 kcal mole, allowing for fast and efficient homogeneous NAD particle production in the stratosphere. However, NAT germ formation energies are large (greater than 26 kcal mole) enough to prevent efficient NAT particle production in the stratosphere. We show that the atmospheric NAD particle production rates based on the surface rate theory are roughly 2 orders of magnitude larger than those obtained from a standard volume-based rate theory. Atmospheric volume and surface production of NAD particles will nearly cease in the stratosphere when denitrification in the air exceeds 40 and 78%, respectively. We show that a surface-based (volume-based) homogeneous freezing rate theory gives particle production rates, which are (not) consistent with both laboratory and atmospheric data on the nucleation of solid polar stratospheric cloud particles.

Tabazadeh, A.↗

Microphysical Modelling of the 1999-2000 Arctic Winter: Impact of Homogeneous Freezing on PSCs - 3

Simulations of the 1999-2000 winter have tested the effect on polar stratospheric clouds (PSCs) of the homogeneous freezing of liquid ternary solutions into nitric acid trihydrate (NAT) and nitric acid dihydrate (NAD). Proposed laboratory-derived volume-based and surface-based homogeneous freezing rates have both been examined, including different assumptions about the extrapolation of laboratory measurements to atmospheric conditions. Widespread PSC formation and denitrification are possible in several of the scenarios examined. However, the simulations are all unable to explain the solid-phase PSCs observed early in the 1999-2000 winter, and are unable to reproduce the measured extent of vortex denitrification. These problems can both be attributed to the relatively cold temperatures, more than 5 K below the NAT condensation point, necessary for effective homogeneous freezing. Therefore synoptic-scale homogeneous freezing appears unlikely to be the primary mechanism responsible for solid-phase PSC formation.

Drdla, K.↗

Emission control system

Methods and apparatus utilizing hydrogen peroxide are useful to reduce NOx, SOx and mercury (or other heavy metal) emissions from combustion flue gas streams. Continuous concentration of hydrogen peroxide to levels approaching or exceeding propellant-grade hydrogen peroxide facilitates increased system efficiency. In this manner, combustion flue gas streams can be treated for the removal of NOx, SOx and heavy metals, while isolating useful by-products streams of sulfuric acid and nitric acid as well as solids for the recovery of the heavy metals.

Parrish, Clyde F.↗

Pretreatment Solution for Water Recovery Systems

Chemical pretreatments are used to produce usable water by treating a water source with a chemical pretreatment that contains a hexavalent chromium and an acid to generate a treated water source, wherein the concentration of sulfate compounds in the acid is negligible, and wherein the treated water source remains substantially free of precipitates after the addition of the chemical pretreatment. Other methods include reducing the pH in urine to be distilled for potable water extraction by pretreating the urine before distillation with a pretreatment solution comprising one or more acid sources selected from a group consisting of phosphoric acid, hydrochloric acid, and nitric acid, wherein the urine remains substantially precipitate free after the addition of the pretreatment solution. Another method described comprises a process for reducing precipitation in urine to be processed for water extraction by mixing the urine with a pretreatment solution comprising hexavalent chromium compound and phosphoric acid.

Muirhead, Dean↗

One Step Plasma Passivation and Precision Cleaning

Over the past several years, Kennedy Space Center (KSC) researchers developed two solvent-free techniques for precision cleaning of ground support equipment (GSE) that possess low commodity requirements and produce small or no waste streams. During testing of low-pressure air plasma as one of these cleaning techniques, physical changes in the surface of stainless steel test pieces were observed; cursory testing revealed that the test part had developed a thick oxide layer on the surface compared to untreated parts. This result indicated that the plasma process might not only serve as a green technology for precision cleaning of parts, but it may also passivate the surface at the same time. Current methodology in use at KSC’s Components Refurbishment & Chemical Analysis (CRCA) Facility for passivation of corrosion-resistant steels for aerospace applications follows an SAE International Standard, AMS2700, where parts are submerged in either a nitric acid or nitric acid/sodium dichromate bath at predetermined temperatures and contact times. These baths require constant testing to ensure effective treatment, use corrosive and carcinogenic chemicals, and produce hazardous waste. The passivation bath is one of the multiple steps employed at the facility, while cleaning with multiple environmentally-unfriendly solvents comprise several more steps before parts are recertified to a specific cleanliness level in their clean room. Based on the behavior of the stainless steel surface during cleaning optimization studies, it was believed that the plasma technology could be extended to passivation, combining what is currently many steps into a single, solvent- and waste-free system.

Paul Hintze↗

File Specification for MERRA-2 Stratospheric Composition Reanalysis of Aura MLS (M2-SCREAM)

This document provides a brief description of the output collections from the MERRA-2 Stratospheric Composition Reanalysis of the Aura Microwave Limb Sounder (M2-SCREAM) produced at NASA’s Global Modeling and Assimilation Office. These data are generated by assimilating retrievals from the Microwave Limb Sounder (MLS) and the Ozone Monitoring Instrument (OMI) into the Global Earth Observing System (GEOS) Constituent Data Assimilation System (CoDAS) driven by meteorological fields from MERRA-2. M2-SCREAM assimilates hydrochloric acid (HCl), nitric acid (HNO3), stratospheric water vapor (H2O), nitrous oxide (N2O) and ozone with a system equipped with a version of the GEOS general circulation model and a stratospheric chemistry model, StratChem. Assimilated fields are provided globally at 0.5° by 0.625° resolution at three-hourly frequencies from 2004/09/01 to 2021. Assimilation uncertainties for each of the assimilated constituents are calculated from the CoDAS statistical output (Wargan et al., 2022) and provided as global full-resolution three-dimensional monthly files.

Krzysztof Wargan↗

Antarctic ozone - Meteoric control of HNO3

Atmospheric circulation leads to an accumulation of debris from meteors in the Antarctic stratosphere at the beginning of austral spring. The major component of meteoric material is alkaline, comprised predominantly of the oxides of magnesium and iron. These metals may neutralize the natural acidity of stratospheric aerosols, remove nitric acid from the gas phase, and bond it as metal nitrates in the aerosol phase. Removal of nitric acid vapor has been previously shown to be a critical link in the photochemical depletion of ozone in the Antarctic spring, by allowing for increased catalytic loss from chlorine and bromine.

Prather, Michael J.↗