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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.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1984

Mechanism for forming hydrogen chloride and sodium sulfate from sulfur trioxide, water, and sodium chloride

A molecular orbital study of sodium sulfate and hydrogen chloride formation from sulfur trioxide, water, and sodium chloride shows no activation barrier, in agreement with recent experimental work of Kohl, Fielder, and Stearns. Two overall steps are found for the process. First, gas-phase water reacts with sulfur trioxide along a pathway involving a linear O-H-O transition state yielding closely associated hydroxyl and bisulfite which rearrange to become a hydrogen sulfate molecule. Then the hydrogen sulfate molecule transfers a hydrogen atom to a surface chloride in solid sodium chloride while an electron and a sodium cation simultaneously transfer to yield sodium bisulfate and gas-phase hydrogen chloride. This process repeats. Both of these steps represent well-known reactions for which mechanisms have not been previously determined.

Anderson, A. B.↗
NASA NTRS1997

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.↗
NASA NTRS1977

Formation of Na2SO4 and K2SO4 in flames doped with sulfur and alkali chlorides and carbonates

High pressure, free-jet expansion, mass spectrometric sampling was used to identify directly and to measure reaction products formed in doped methane-oxygen flames. Flames were doped with SO2 or CH3SH and sodium or potassium chlorides or carbonates. Gaseous NA2SO4 or K2S04 molecules were formed in residence times on the order of msec for each combination of dopants used. Composition profiles of combustion products were measured and compared with equilibrium thermodynamic calculations of product composition.

Fryburg, G. C.↗
NASA NTRS1977

Formation of Na2SO4 and K2SO4 in flames doped with sulfur and alkali chlorides and carbonates

High pressure, free-jet expansion, mass spectrometric sampling was used to identify directly and to measure reaction products formed in doped methane-oxygen flames. Flames were doped with SO2 or CH3SH and sodium or potassium chlorides or carbonates. Gaseous Na2SO4 or K2SO4 molecules were formed in residence times on the order of 1 msec for each combination of dopants used. Composition profiles of combustion products were measured and compared with equilibrium thermodynamic calculations of product composition.

Fryburg, G. C.↗
NASA NTRS1975

Thermochemical cycles

The thermochemical production of hydrogen is described along with the HYDRGN computer program which attempts to rate the various thermochemical cycles. Specific thermochemical cycles discussed include: iron sulfur cycle; iron chloride cycle; and hybrid sulfuric acid cycle.

Funk, J. E.↗
NASA NTRS1991

NASA Li/CF(x) cell problem analysis: Anion exchange chromatography analysis

An analysis was made of wiper samples used to wipe down lithium/chlorine fluorine battery components and production equipment. These components and equipment were potentially exposed to thionyl chloride vapors. In the presence of moisture, thionyl chloride decomposes to sulfur dioxide and hydrogen chloride. The wiper samples were analyzed for soluble chlorides and fluorides by anion exchange chromatography. During the examination of the test chromatographs, fluoride contamination was discovered in wiper samples from the test equipment. An analytical method to determine fluoride was developed. The first 3 extracts from the potentially exposed and clean wiper samples were tested, and the total fluoride from both groups determined. A comparison of the results from both groups was made to determine the extent of fluoride contamination.

Bytella, Joseph↗
NASA NTRS1977

Analytical methods for toxic gases from thermal degradation of polymers

Toxic gases evolved from the thermal oxidative degradation of synthetic or natural polymers in small laboratory chambers or in large scale fire tests are measured by several different analytical methods. Gas detector tubes are used for fast on-site detection of suspect toxic gases. The infrared spectroscopic method is an excellent qualitative and quantitative analysis for some toxic gases. Permanent gases such as carbon monoxide, carbon dioxide, methane and ethylene, can be quantitatively determined by gas chromatography. Highly toxic and corrosive gases such as nitrogen oxides, hydrogen cyanide, hydrogen fluoride, hydrogen chloride and sulfur dioxide should be passed into a scrubbing solution for subsequent analysis by either specific ion electrodes or spectrophotometric methods. Low-concentration toxic organic vapors can be concentrated in a cold trap and then analyzed by gas chromatography and mass spectrometry. The limitations of different methods are discussed.

Hsu, M.-T. S.↗
NASA NTRS1985

Molecular orbital studies in oxidation: Sulfate formation and metal-metal oxide adhesion

The chemical mechanisms for sulfate formation from sodium chloride and sulfur trioxide, which is a product of jet fuel combustion was determined. Molten sodium sulfate leads to hot corrosion of the protective oxide layers on turbine blades. How yttrium dopants in nidkel-aluminum alloys used in turbine blades reduce the spalling rate of protective alumina films and enhance their adhesion was also determined. Two other fulfate mechanisms were deduced and structure of carbon monoxide on a clean chronium and clean platinum-titanium alloys surfaces was determined. All studies were by use of the atom superposition and electron delocalization molecular orbital (ASED-MO) theory. Seven studies were completed. Their titles and abstracts are given.

Anderson, A. B.↗
NASA NTRS1986

Molten salt corrosion of SiC and Si3N4

The most severe type of corrosion encountered in heat engines is corrosion by molten sodium sulfate, formed by the reaction of ingested sodium chloride and sulfur impurities in the fuel. This problem was studied extensively for superalloys, but only recently examined for ceramics. This problem is addressed with laboratory studies to understand the fundamental reaction mechanisms and with burner studies to provide a more realistic simulation of the conditions encountered in a heat engine. In addition the effect of corrosion on the strengths of these materials was assessed. Each of these aspects will be reviewed and some ideas toward possible solutions will be discussed.

Jacobson, N. S.↗
NASA NTRS1988

Heterogeneous interactions of chlorine nitrate, hydrogen chloride, and nitric acid with sulfuric acid surfaces at stratospheric temperatures

The heterogeneous interactions of ClONO2, HCl, and HNO3 with sulfuric acid surfaces were studied using a Knudsen cell flow reactor. The surfaces studied, chosen to simulate global stratospheric particulate, were composed of 65-75 percent H2SO4 solutions at temperatures in the range -63 to -43 C. Heterogeneous loss, but not reaction, of HNO3 and HCl occurred on these surfaces; the measured sticking coefficients are reported. Chlorine nitrate reacted on the cold sulfuric acid surfaces, producing gas-phase HOCl and condensed HNO3. CLONO2 also reacted with HCl dissolved in the 65-percent H2SO4 solution at -63 C, forming gaseous Cl2. In all cases studied, the sticking and/or reaction coefficients were much larger for the 65-percent H2SO4 solution at -63 C than for the 75-percent solution at -43 C.

Tolbert, Margaret A.↗
NASA NTRS1998

Fourier Transform Infrared (FT-IR) Spectroscopy of Atmospheric Trace Gases HCl, NO and SO2

Fourier Transform Infrared (FT-IR) spectral data have been recorded in the spectral region 400-4000/cm of hydrogen chloride and sulfur dioxide with I/cm resolution and of nitric oxide with 0.25 cm-i resolution, under quasi-static conditions, when the sample gas was passed through tubings of aluminum, copper, stainless steel and teflon. The absorbance was measured for the rotational lines of the fundamental bands of (1)H(35)Cl and (1)H(37)Cl for pressures in the range 100-1000 Torr and for the (14)N(16)O molecule in the range 100-300 Torr. The absorbance was also measured for individual rotational lines corresponding to the three modes of vibrations (upsilon(sub 1) - symmetric stretch, upsilon(sub 2) - symmetric bend, upsilon(sub 3) - anti-symmetric stretch) of the SO2 molecule in the pressure range 25-150 Torr. A graph of absorbance versus pressure was plotted for the observed rotational transitions of the three atmospherically significant molecules, and it was found that the absorbance was linearly proportional to the pressure range chosen, thereby validating Beer's law. The absorption cross-sections were determined from the graphical slopes for each rotational transition recorded for the HCl, NO and SO2 species. Qualitative and quantitative spectral changes in the FT-IR data will be discussed to identify and characterize various tubing materials with respect to their absorption features.

Haridass, C.↗
NASA NTRS1999

Electrochemical Measurement of Atmospheric Corrosion

Corrosion of Shuttle thruster components in atmospheres containing high concentrations of nitrogen tetroxide (NTO) and water is an important issue in ground operations of bipropellant systems in humid locations. Measurements of the corrosivities of NTO-containing atmospheres and the responses of different materials to these atmospheres have been accomplished using an electrochemical sensor. The sensor is composed of alternating aluminum/titanium strips separated by thin insulating layers. Under high humidity conditions a thin film of water covers the surface of the sensor. Added NTO vapor reacts with the water film to form a conductive medium and establishes a galvanic cell. The current from this cell can be integrated with respect to time and related to the corrosion activity. The surface layer formed from humid air/NTO reacts in the same way as an aqueous solution of nitric acid. Nitric acid is generally considered an important agent in NTO corrosion situations. The aluminum/titanium sensor is unresponsive to dry air, responds slightly to humid air (> 75% RH), and responds strongly to the combination of humid air and NTO. The sensor response is a power function (n = 2) of the NTO concentration. The sensor does not respond to NTO in dry air. The response of other materials in this type of sensor is related to position of the material in a galvanic series in aqueous nitric acid. The concept and operation of this electrochemical corrosion measurement is being applied to other corrosive atmospheric contaminants such as hydrogen chloride, hydrogen fluoride, sulfur dioxide, and acidic aerosols.

DeArmond, Anna H.↗
NASA NTRS1982

Small particles in plumes of Mount St. Helens

Particles in the size range 0.1-25 microns were sampled by aircraft carrying a quartz crystal microcascade in the Mount St. Helens plume on three dates in August and September 1980. Two of the sampling dates represented 'typical' emissions of the volcano between plinian eruptions. One sampling flight was made 1-4 hours before the small plinian eruption of August 7, 1980 when the plume had become discontinuous and visibly darker. The plume sampled on August 7, before the eruption, contained mainly approximately 2-micron diameter silicic glass particles, fragments of the Mount St. Helens magma. The typical plumes sampled on September 22 and August 6 had much smaller concentrations of particles, trimodal size distributions with peaks at 10, 0.4, and 0.1 microns. The particles were largely nonsilicate and apparently represented Cu-Zn oxide (10 micron peak), Al sulfate, chloride, and oxide, and sulfuric acid (smallest size peak).

Rose, W. I.↗
NASA NTRS1988

Collisions with ice-volatile objects: Geological implications

The collision of the Earth with extra-terrestrial ice-volatile bodies is proposed as a mechanism to produce rapid changes in the geologic record. These bodies would be analogs of the ice satellites found for the Jovian planets and suspected for comets and certain low density bodies in the Asteroid belt. Five generic end-members are postulated: (1) water ice; (2) dry ice: carbon-carbon dioxide rich, (3) oceanic (chloride) ice; (4) sulfur-rich ice; (5) ammonia hydrate-rich ice; and (6) clathrate: methane-rich ice. Due to the volatile nature of these bodies, evidence for their impact with the Earth would be subtle and probably best reflected geochemically or in the fossil record. Actual boloids impacting the Earth may have a variable composition, generally some admixture with water ice. However for discussion purposes, only the effects of a dominant component will be treated. The general geological effects of such collisions, as a function of the dominant component would be: (1) rapid sea level rise unrelated to deglaciation, (2) decreased oceanic pH and rapid climatic warming or deglaciation; (3) increased paleosalinities; (4) increased acid rain; (5) increased oceanic pH and rapid carbonate deposition; and (6) rapid climatic warming or deglaciation.

Wilde, P.↗
NASA NTRS1982

Friction and Wear of Iron in Corrosive Media

Friction and wear experiments were conducted with elemental iron exposed to various corrosive media including two acids, base, and a salt. Studies involved various concentrations of nitric and sulfuric acids, sodium hydroxide, and sodium chloride. Load and reciprocating sliding speed were kept constant. With the base NaOH an increase in normality beyond 0.01 N resulted in a decrease in both friction and wear. X-ray photoelectron spectroscopy (XPS) analysis of the surface showed a decreasing concentration of ferric oxide (Fe2O3) on the iron surface with increasing NaOH concentration. With nitric acid (HNO3) friction decreased in solutions to 0.05 N, beyond which no further change in friction was observed. The concentration of Fe2O3 on the surface continued to increase with increasing normality. XPS analysis revealed the presence of sulfates in addition of Fe2O3 on surfaces exposed to sulfuric acid and iron chlorides but no sodium on surfaces exposed to NaCl.

Rengstorff, G. W. P.↗
NASA NTRS1996

Heterogeneous Chemistry of HONO on Liquid Sulfuric Acid: A New Mechanism of Chlorine Activation on Stratospheric Sulfate Aerosols

Heterogeneous chemistry of nitrous acid (HONO) on liquid sulfuric acid (H2SO4) Was investigated at conditions that prevail in the stratosphere. The measured uptake coefficient (gamma) of HONO on H2SO4 increased with increasing acid content, ranging from 0.03 for 65 wt % to about 0.1 for 74 wt %. In the aqueous phase, HONO underwent irreversible reaction with H2SO4 to form nitrosylsulfuric acid (NO(+)HSO4(-). At temperatures below 230 K, NO(+)HSO4(-) was observed to be stable and accumulated in concentrated solutions (less than 70 wt % H2SO4) but was unstable and quickly regenerated HONO in dilute solutions (less than 70 wt %). HCl reacted with HONO dissolved in sulfuric acid, releasing gaseous nitrosyl chloride (ClNO). The reaction probability between HCl and HONO varied from 0.01 to 0.02 for 60-72 wt % H2SO4. In the stratosphere, ClNO photodissociates rapidly to yield atomic chlorine, which catalytically destroys ozone. Analysis of the laboratory data reveals that the reaction of HCl with HONO on sulfate aerosols can affect stratospheric ozone balance during elevated sulfuric acid loadings after volcanic eruptions or due to emissions from the projected high-speed civil transport (HSCT). The present results may have important implications on the assessment of environmental acceptability of HSCT.

Zhang, Renyi↗