Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “hydroxide anions”

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.

15 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS2007

Iron Mineralogy and Aqueous Alteration on Mars from the MER Moessbauer Spectrometers

The twin Mars Exploration Rovers Spirit (Gusev crater) and Opportunity (Meridiani Planum) used MIMOS II Moessbauer spectrometers to analyze martian surface materials in the first application of extraterrestrial Moessbauer spectroscopy. The instruments acquired spectra that identified the speciation of Fe according to oxidation state, coordination state, and mineralogical composition and provided quantitative information about the distribution of Fe among oxidation states, coordination states, and Fe-bearing phases. A total of 12 unique Fe-bearing phases were identified: Fe(2+) in olivine, pyroxene, and ilmenite; Fe(2+) and Fe(3+) in magnetite and chromite; Fe(3+) in nanophase ferric oxide (npOx), hematite, goethite, jarosite, an unassigned Fe3+ sulfate, and an unassigned Fe(3+) phase associated with jarosite; and Fe(0) in kamacite. Weakly altered basalts at Gusev crater (SO3 = 2.5 +/- 1.4 wt.% and Fe(3+)/Fe(sub T) = 0.24 +/- 0.11) are widespread on the Gusev plains and occur in less abundance on West Spur and Husband Hill in the Columbia Hills. Altered low-S rocks (SO3 = 5.2 +/- 2.0 wt.% and Fe(3+)/Fe(sub T) = 0.63 +/- 0.18) are the most common type of rock in the Columbia Hills. Ilm-bearing, weakly altered basalts were detected only in the Columbia Hills, as was the only occurrence of chromite in an altered low-S rock named Assemblee. Altered high-S rocks (SO3 > 14.2 wt.% and Fe(3+)/Fe(sub T) = 0.83 +/- 0.05) are the outcrop rocks of the ubiquitous Burns formation at Meridiani Planum. Two Fe(0)-bearing rocks at Meridiani Planum (Barberton and Heat Shield Rock) are meteorites. Laguna Class soil is weakly altered (SO3 = 6 +/- 2 wt.% and Fe(3+)/Fe(sub T) = 0.29 +/- 0.08) and widely distributed at both Gusev crater and Meridiani Planum, implying efficient global mixing processes or a global distribution of precursor rocks with comparable Fe mineralogical compositions. Paso Robles Class soil is heavily altered (SO3 approx. 31 wt.% and Fe(3+)/Fe(sub T) = 0.83 +/- 0.05), is relatively uncommon, and occurs as subsurface deposits in the Columbia Hills. Berry Class soil is also heavily altered (SO3 = 5 +/- 1 wt.% and Fe(3+)/Fe(sub T) = 0.60 +/- 0.13) and occurs at Meridiani Planum as lag deposits, at the crests of aeolian bedforms, and as isolated pockets on outcrop surfaces. Magnetite is identified as the strongly magnetic component in martian soil. Jarosite (in the Burns outcrop at Meridiani Planum) and goethite (in Clovis Class rocks at Gusev crater) are mineralogical markers for aqueous processes because they contain the hydroxide anion (OH(-)) as an essential part of their structure. Each yields approx.10 wt.% H2O upon dehydroxylation. The presence of Fe sulfates on opposite sides of Mars is evidence that aqueous processes under acid sulfate conditions are or were common. Except for Independence Class rocks in the Columbia Hills, the overall Fe mineralogical compositions and similar basaltic bulk chemical compositions (calculated with respect to S = Cl = 0) of the population of altered rocks analyzed by MER imply isochemical alteration of basaltic precursors at low water-to-rock ratios.

Morris, Richard V.↗
NASA NTRS2006

Fe-Bearing Phases Identified by the Moessbauer Spectrometers on the Mars Exploration Rovers: An Overview

The twin Mars Exploration Rovers Spirit and Opportunity have explored the martian surface at Gusev Crater (GC) and Meridiani Planum (MP), respectively, for about two Earth years. The Moessbauer (MB) spectrometers on both rovers have analyzed an aggregate of ~200 surface targets and have returned to Earth information on the oxidation state of iron, the mineralogical composition of Febearing phases, and the distribution of Fe among oxidation states and phases at the two landing sites [1-7]. To date, 15 component subspectra (10 doublets and 5 sextets) have been identified and most have been assigned to mineralogical compositions. Two subspectra are assigned to phases (jarosite and goethite) that are marker minerals for aqueous processes because they contain hydroxide anion in their structures. In this paper, we give an overview of the Febearing phases identified and their distributions at Gusev crater and Meridiani Planum.

Morris, R. V.↗
NASA NTRS2006

Fe-Bearing Phases Indentified by the Moessbauer Spectrometers on the Mars Exploration Rovers: An Overview

The twin Mars Exploration Rovers Spirit and Opportunity have explored the martian surface at Gusev Crater (GC) and Meridiani Planum (MP), respectively, for about two Earth years. The Moessbauer (MB) spectrometers on both rovers have analyzed an aggregate of approx.200 surface targets and have returned to Earth information on the oxidation state of iron, the mineralogical composition of Fe-bearing phases, and the distribution of Fe among oxidation states and phases at the two landing sites [1-7]. To date, 15 component subspectra (10 doublets and 5 sextets) have been identified and most have been assigned to mineralogical compositions. Two subspectra are assigned to phases (jarosite and goethite) that are marker minerals for aqueous processes because they contain hydroxide anion in their structures. In this paper, we give an overview of the Febearing phases identified and their distributions at Gusev crater and Meridiani Planum.

Morris, R. V.↗
NASA NTRS2012

Imidazolium-Based Polymeric Materials as Alkaline Anion-Exchange Fuel Cell Membranes

Polymer electrolyte membranes that conduct hydroxide ions have potential use in fuel cells. A variety of polystyrene-based quaternary ammonium hydroxides have been reported as anion exchange fuel cell membranes. However, the hydrolytic stability and conductivity of the commercially available membranes are not adequate to meet the requirements of fuel cell applications. When compared with commercially available membranes, polystyrene-imidazolium alkaline membrane electrolytes are more stable and more highly conducting. At the time of this reporting, this has been the first such usage for imidazolium-based polymeric materials for fuel cells. Imidazolium salts are known to be electrochemically stable over wide potential ranges. By controlling the relative ratio of imidazolium groups in polystyrene-imidazolium salts, their physiochemical properties could be modulated. Alkaline anion exchange membranes based on polystyrene-imidazolium hydroxide materials have been developed. The first step was to synthesize the poly(styrene-co-(1-((4-vinyl)methyl)-3- methylimidazolium) chloride through a free-radical polymerization. Casting of this material followed by in situ treatment of the membranes with sodium hydroxide solutions provided the corresponding hydroxide salts. Various ratios of the monomers 4-chloromoethylvinylbenzine (CMVB) and vinylbenzine (VB) provided various compositions of the polymer. The preferred material, due to the relative ease of casting the film, and its relatively low hygroscopic nature, was a 2:1 ratio of CMVB to VB. Testing confirmed that at room temperature, the new membranes outperformed commercially available membranes by a large margin. With fuel cells now in use at NASA and in transportation, and with defense potential, any improvement to fuel cell efficiency is a significant development.

Narayan, Sri R.↗
NASA NTRS2000

Concentration of simple aldehydes by sulfite-containing double-layer hydroxide minerals: implications for biopoesis

Environmental conditions play an important role in conceptual studies of prebiotically relevant chemical reactions that could have led to functional biomolecules. The necessary source compounds are likely to have been present in dilute solution, raising the question of how to achieve selective concentration and to reach activation. With the assumption of an initial 'RNA World', the questions of production, concentration, and interaction of aldehydes and aldehyde phosphates, potential precursors of sugar phosphates, come into the foreground. As a possible concentration process for simple, uncharged aldehydes, we investigated their adduct formation with sulfite ion bound in the interlayer of positively charged expanding-sheet-structure double-layer hydroxide minerals. Minerals of this type, initially with chloride as interlayer counter anion, have previously been shown to induce concentration and subsequent aldolization of aldehyde phosphates to form tetrose, pentose, and hexose phosphates. The reversible uptake of the simple aldehydes formaldehyde, glycolaldehyde, and glyceraldehyde by adduct formation with the immobilized sulfite ions is characterized by equilibrium constants of K=1.5, 9, and 11, respectively. This translates into an observable uptake at concentrations exceeding 50 mM.

NASA Discipline Exobiology↗
NASA NTRS1982

Adsorption of humic acids and trace metals in natural waters

Studies concerning the interactions between suspended hydrous iron oxide and dissolved humic acids and trace metals are reported. As a major component of dissolved organic matters and its readiness for adsorption at the solid/water interface, humic acids may play a very important role in the organometallic geochemistry of suspended sediments and in determining the fate and distribution of trace metals, pesticides and anions in natural water systems. Most of the solid phases in natural waters contain oxides and hydroxides. The most simple promising theory to describe the interactions of hydrous iron oxide interface is the surface complex formation model. In this model, the adsorptions of humic acids on hydrous iron oxide may be interpreted as complex formation of the organic bases (humic acid oxyanions) with surface Fe ions. Measurements on adsorptions were made in both fresh water and seawater. Attempts have been made to fit our data to Langmuir adsorption isotherm. Adsorption equilibrium constants were determined.

Leung, W. H.↗
NASA NTRS2018

Reaction of Akaganeite with Mars-Relevant Anions

Akaganeite has been identified by the Chemistry and Mineralogy (CheMin) and Sample Analysis at Mars (SAM) instruments onboard the Curiosity rover in Yellowknife Bay, Gale Crater, Mars. Akaganeite was also detected by the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) instrument on the Mars Reconnaissance Orbiter (MRO) in Robert Sharp Crater and Antoniadi basin. Akaganeite is an iron(III) hydroxide with a hollandite-like tunnel structure with tunnels usually occupied by Cl-. Chloride in tunnels is not immobile and can be replaced by other anions in solution. Identification of tunnel composition with Mars-like instruments can help to characterize composition of ancient aqueous environments where akaganeite is present on Mars.

Pan, M. J.↗
NASA NTRS1999

The Thermal Emission Imaging System (THEMIS) Instrument for the Mars 2001 Orbiter

The primary objective of the Thermal Emission Imaging System (THEMIS) on the Mars Surveyor '01 Orbiter is to study the composition of the Martian surface at high spatial resolution. THEMIS will map the surface mineralogy using multi-spectral thermal infrared images in 8 spectral bands from 6.5 to 14.5 microns. In addition, a band centered at 15 microns will be used to map atmospheric temperatures and provide an important aid in separating the surface and atmospheric components. The entire planet will be mapped at 100 m resolution within the available data volume using a multi-spectral, rather than hyperspectral, imaging approach. THEMIS will also acquire 20 m resolution visible images in up to 5 spectral bands using a replica of the Mars 98 Orbiter (MARCI) and Lander (MARDI) cameras. Over 15,000 panchromatic (3,000 5-color), 20 x 20 km images will be acquired for morphology studies and landing site selection. The thermal-infrared spectral region contains the fundamental vibrational absorption bands of most minerals which provide diagnostic information on mineral composition. All geologic materials, including carbonates, hydrothermal silica, sulfates, phosphates, hydroxides, silicates, and oxides have strong absorptions in the 6.5-14.5 micron region. Silica and carbonates, which are key diagnostic minerals in thermal spring deposits, are readily identified using thermal-IR spectra. In addition, the ability to identify all minerals allows the presence of aqueous minerals to be interpreted in the proper geologic context. An extensive suite of studies over the past 35 years has demonstrated the utility of vibrational spectroscopy for the quantitative determination of mineralogy and petrology. The fundamental vibrations within different anion groups, such as C03, S04, P04, and SiO4, produce unique, well separated spectral bands that allow carbonates, sulfates, phosphates, silicates, oxides, and hydroxides to be readily identified. Additional stretching and bending modes involving major cations, such as Mg, Fe, Ca, and Na, allow Further mineral identification, such as the excellent discriminability of minerals within the silicate and carbonate groups.

Christensen, P. R.↗
NASA NTRS1994

Double layer hydroxide minerals as host structures for bioorganic molecules

A central problem in molecular evolution concerns the selective concentration from dilute, multicomponent solution of source molecules into a reactive environment, where formation of larger molecular assemblages can take place. Minerals consisting of positively charged, separable metal hydroxide sheets have proven capable of these functions. This common structural type is represented by minerals such as pyroaurite (Mg-Fe(3+) hydroxide), hydrotalcite (Mg-Al), green rust Fe(2+)-Fe(3+) and others. Effective interlayer sorption is demonstrated for orthophosphate and condensed phosphates, anionic alkyl compounds, polypeptides, nucleic acids, cyanide complexes and glycolaldehyde phosphate, the latter shown to readily oligomerize to form and selectively retain racemic hexose -2, 4, 6-phosphates, preferentially of altrose (Pitsch, et al, 1993). The selective aldomerization and retention effects correlate with the charge distribution in the host mineral structure and the stereochemistry of the substrate molecules. Interaction between nucleic acid bases, and between the cyanide groups of glycolaldehyde phosphate nitrile at the low water activity in the mineral interlayer is indicated by doubling of the monomeric separation of the hydroxide mineral sheets.

Lee, Ton↗
NASA NTRS1996

Effect of KOH Concentration and Anions on the Performance of a Ni-H2 Battery Positive Plate

The capacity and voltage behavior of electrochemically impregnated sintered nickel positive plates was examined by galvanostatic charging and discharging in a flooded electrolyte cell. Three different concentrations of potassium hydroxide (KOH) (40, 31, and 26 percent) and 31 percent KOH containing dissolved nitrate, sulfate, or silicate were investigated. The end-of-charge voltage at C/10 charge and at 10 degrees C showed the following order: 40 percent KOH greater than 31 percent KOH alone and in the presence of the anions greater than 26 percent KOH. The mid discharge voltage at C/2 discharge was higher in 26 percent KOH, almost the same for 31 percent KOH with and without added contaminants, and much lower for 40 percent KOH. The plate capacity was marginally affected by cycling in all cases except for 40 percent KOH, where the capacity declined after 1,000 cycles at 80 percent depth of discharge (DOD). At the end of cycling, all the plates tested experienced a weight loss, except in the case of 31 percent KOH, as a result of active material extrusion. Cyclic voltammetry of miniature electrodes in 31 percent KOH showed that the cathodic peak potentials are less polarized in the presence and absence of silicate at -5 degrees C compared to 25 degrees C indicating a slightly higher voltage during discharge in a Ni-H2 battery. Futhermore, the features of the current-potential profile were practically unchanged in the presence of silicate.

Vaidyanathan, Hari↗
NASA NTRS2018

Topological Control of Polystyrene-Silica Core-Shell Microspheres

Controllable surface morphology is requisite across a gamut of processes, industries, and applications. The surface morphology of silica-coated polystyrene microspheres was controllably modified to enable generation of both smooth and bumpy, or raspberry-like, surfaces. Although smooth and raspberry-like silica shells on polystyrene templates have been demonstrated extensively, the method described here used readily available materials to produce radical changes in surface morphology from a single polystyrene template coated in silica through a facile sol-gel reaction processes. Silica shells were deposited via a sol-gel process (using tetraethyl orthosilicate as the silica precursor) onto 1 to 2 m diameter anionic polystyrene spheres, fabricated by emulsifier-free polymerization. By varying of the concentration of silica precursor and ammonium hydroxide catalyst and altering the electrostatic surface interactions via addition of a cationic polymeric brush, an array of surface topologies was generated. The resulting silica shells ranged from 100 to 200 nm in thickness, as measured by calcination of the polystyrene template. Empirical relations between reaction conditions and the resulting silica colloid diameter were utilized to understand the resultant silica shell topology. These results may serve as a guide to generate a versatile platform for research in the multitude of applications where polystyrene-silica core-shell particles are utilized.

Zane A. Grady↗
NASA NTRS1992

Spectral identification of chemisorbed CO2 and application to Mars analog materials

The goal of this work is to identify the spectral signature of chemisorbed CO2, to test the efficacy of carbonate formation on Mars-analog materials via CO2 chemisorption, and to identify the surface-chemical characteristics of good chemisorbents, with the intent of assessing the possible geochemical importance of CO2 chemisorption as a quasipermanent CO2 sink in the Martian environment. Our approach is to search for infrared spectral bands that result from chemisorption of CO2 molecules onto chemical reagents and Mars-analog materials, and to identify the salient differences in adsorbents that favor strong, permanent CO2 chemisorption. The total amount of CO2 in the early Martian atmosphere, and consequent surface temperatures, are unknown. A CO2 greenhouse may not have been an adequate mechanism under any circumstances; however, it if were, then most of that CO2 must still be in the near-surface environment; no escape mechanism that could remove it after the decline of channeling has been identified. The only plausible reservoir is carbonate, and there are various remote sensing techniques that can be used to search for it. We are investigating CO2 chemisorption as a permanent CO2 sink, and to aid in interpretation of remotely sensed IR spectra of Mars. A common effect reported in CO2 adsorption studies is the formation of a layer of carbonate or bicarbonate anions on adsorbents that have OH- groups available on their surfaces. Inorganic hydroxyls occur on phyllosilicates, amorphous silicates, metal oxides and hydroxides; it is the most abundant and reactive surface functional group on the surfaces of terrestrial silicates. The process responsible for the reaction is chemisorption. Chemisorption is distinguished from physical adsorption in that there is a transfer of electrons between species, and the formation of a chemical bond. The heat of chemisorption is typically of the same order as heats of chemical reaction (i.e., a few hundred to a few thousand kJ/mole), as opposed to heats of physical adsorption (a few kJ per mole). Chemisorption is an activated process that is promoted by an increase in temperature - quite the opposite of physical adsorption. Chemisorption is not reversible in the sense that physical adsorption is.

Zent, A. P.↗
NASA NTRS1989

Mixed-valence hydroxides as bioorganic host minerals

A range of naturally occurring divalent-trivalent metal cation hydroxides and modified artifical analogs have been synthesized and characterized. Structural and chemical properties of these minerals, determining their capability to selectively concentrate, order and alter molecules of prebiotic interest, include their anion exchange capacity and specificity, photochemical reactivity, production of nascent hydrogen, and catalytic efficiency. Properties relevant to these functions have been investigated and are discussed.

Kuma, K.↗
NASA NTRS2005

Abundance and Speciation of Water and Sulfate at Gusev Crater and Meridiani Planum

A major science goal of the Mars Exploration Rover (MER) mission is to search for evidence of water activity, and direct mineralogical evidence for aqueous activity has been reported for Meridiani Planum in the form of the iron sulfate hydroxide mineral jarosite and at Gusev crater in the form of goethite. The Spirit and Opportunity rovers have each collected 110+ Moessbauer (MB) and 75+ Alpha Particle X-Ray Spectrometer (APXS) spectra from Gusev crater and Meridiani Planum [1 - 4]. In this abstract, we use mineralogical and elemental data, primarily from the Moessbauer and APXS instruments, to infer the speciation and estimate the abundance of sulfate and water (as either the H2O molecule or the hydroxyl anion) at Gusev crater and Meridiani Planum. Throughout the abstract, we adopt a format for mineral formulas that shows water explicitly rather than the usual practice of structure-based formulas (e.g., for goethite we write Fe2O3xH2O instead of FeOOH).

Ming, D. W.↗
NASA NTRS1986

Theoretical dissociation energies for ionic molecules

Ab initio calculations at the self-consistent-field and singles plus doubles configuration-interaction level are used to determine accurate spectroscopic parameters for most of the alkali and alkaline-earth fluorides, chlorides, oxides, sulfides, hydroxides, and isocyanides. Numerical Hartree-Fock (NHF) calculations are performed on selected systems to ensure that the extended Slater basis sets employed for the diatomic systems are near the Hartree-Fock limit. Extended Gaussian basis sets of at least triple-zeta plus double polarization equality are employed for the triatomic system. With this model, correlation effects are relatively small, but invariably increase the theoretical dissociation energies. The importance of correlating the electrons on both the anion and the metal is discussed. The theoretical dissociation energies are critically compared with the literature to rule out disparate experimental values. Theoretical (sup 2)Pi - (sup 2)Sigma (sup +) energy separations are presented for the alkali oxides and sulfides.

Langhoff, S. R.↗