Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Chlorine Experiments”

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 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
NASA NTRS1985

Pressure dependence of the absolute rate constant for the reaction Cl + C2H2 from 210-361 K

In recent years, considerable attention has been given to the role of chlorine compounds in the catalytic destruction of stratospheric ozone. However, while some reactions have been studied extensively, the kinetic data for the reaction of Cl with C2H2 is sparse with only three known determinations of the rate constant k3. The reactions involved are Cl + C2H2 yields reversibly ClC2H2(asterisk) (3a) and ClC2H2(asterisk) + M yields ClC2H2 + M (3b). In the present study, flash photolysis coupled with chlorine atomic resonance fluorescence have been employed to determine the pressure and temperature dependence of k3 with the third body M = Ar. Room temperature values are also reported for M = N2. The pressure dependence observed in the experiments confirms the expectation that the reaction involves addition of Cl to the unsaturated C2H2 molecule followed by collisional stabilization of the resulting adduct radical.

Brunning, J.↗
NASA NTRS2000

CCD-Based XRD/XRF for Determining Environmental Mineralogy on Mars

Health effects from Martian dusts will be a concern for any manned Mars missions. Nuisance dusts plagued the Apollo astronauts, but dusts of more hazardous mineralogy, in habitats occupied by Mars astronauts weakened by a long-duration mission, may be more than a nuisance. Chemical hazards in Martian regolith attributable to S, Cl, Br, Cd, and Pb are known or strongly suspected to be present, but terrestrial studies of the health effects of dusts indicate that accurate determination of mineralogy is a critical factor in evaluating inhalation hazards. Mineral inhalation hazards such as the Group-I carcinogenic zeolite erionite, which is demonstrated to cause mesothelioma, cannot be identified by chemical analysis alone. Studies of palagonite analogs raise the possibility that erionite may occur on Mars. In addition to health effects concerns, environmental mineralogy has significant importance in resource extraction, groundwater use, and sustained agriculture. The high sulfur and chlorine content of Martian regolith will affect all of these uses, but the nature of mineralogic reservoirs for S and Cl will determine their uptake and concentration in extracted groundwater and in agricultural applications of regolith. Wet chemistry experiments planned for the Mars Environmental Compatibility Assessment (MECA) will define some of the consequences of water/soil interaction, but an understanding of the mineralogic basis for water-rock reactions is needed to understand the mechanisms of reaction and to apply the results of a few experiments to larger scales and different conditions.

Vaniman, D. T.↗
NASA NTRS1987

Review of water disinfection techniques

Throughout the history of manned space flight the supply of potable water to the astronauts has presented unique problems. Of particular concern has been the microbiological quality of the potable water. This has required the development of both preflight water system servicing procedures to disinfect the systems and inflight disinfectant addition and monitoring devices to ensure continuing microbiological control. The disinfectants successfully used to date have been aqueous chlorine or iodine. Because of special system limitations the use of iodine has been the most successful for inflight use and promises to be the agent most likely to be used in the future. Future spacecraft potable, hygiene, and experiment water systems will utilize recycled water. This will present special problems for water quality control. NASA is currently conducting research and development to solve these problems.

Colombo, Gerald V.↗
NASA NTRS1992

Direct observation of ClO from chlorine nitrate photolysis

Chlorine nitrate photolysis has been investigated with the use of a molecular beam technique. Excitation at both 248 and 193 nanometers led to photodissociation by two pathways, ClONO2 yields ClO + NO2 and ClONO2 yields Cl + NO3, with comparable yields. This experiment provides a direct measurement of the ClO product channel and consequently raises the possibility of an analogous channel in ClO dimer photolysis. Photodissociation of the ClO dimer is a critical step in the catalytic cycle that is presumed to dominate polar stratospheric ozone destruction. A substantial yield of ClO would reduce the efficiency of this cycle.

Minton, Timothy K.↗
NASA NTRS1989

Laboratory chemistry and stratospheric clouds

Results are presented from laboratory experiments on the chemistry of ice particles to study the role of HCl and ClONO2 from CFCs in stratospheric ozone depletion over Antarctica. It is found that gaseous HCl is scavenged with high efficiency by the ice and the gas phase chlorine nitrate may react with the HCL-containing ice to produce Cl2. Also, consideration is given ot the behavior of solid nitric acid trihydrate and sulfuric acid aerosols.

Molina, Mario J.↗
DOE OSTI2025

Novel Electrowinning Reactor for the Energy-Efficient, Low- Cost Production of Rare Earth Metals

This project developed a novel neodymium (Nd) electrowinning reactor for energy-efficient electrowinning of Nd metal. Throughout this project we have developed an alternative chloride based molten salt electrolysis process. Our process lowers the specific electrical energy consumption compared to the state of the art, while producing reusable chlorine gas and eliminating direct CO2 and PFC emissions. Facilities required for implementing the project were setup and designs were finalized, and a standard operating procedure for safe operation of high temperature electrolysis cells was written. The electrowinning reactor was designed and constructed. Electrolysis experiments confirmed the ability to reproducibly electrowin Nd metal on a Mo cathode. The current efficiency for Nd electrowinning was measured as a function of applied current density in the presence of the separator. Successful electrowinning of Nd sponge at high current densities (200 mA/cm2 and above) at a current efficiency >80% was demonstrated using multiple techniques. Stable Nd electrowinning up to 10h at 250 mA/cm2 was demonstrated. All of these design advancements were used to develop a techno-economic and life cycle assessment model that demonstrated that our process could be operated at cost of less than $0.20/kg-Nd (~30% lower compared to state of the art when comparing electrolysis energy cost) with a >20% total reduction in global warming potential compared to the state of the art while generating no direct CO2 or perfluorocarbon emissions.

42 ENGINEERING↗
NASA NTRS1996

Balloon observations of organic and inorganic chlorine in the stratosphere: the role of HClO4 production on sulfate aerosols

Simultaneous observations of stratospheric organic and inorganic chlorine were made in September 1993 out of Fort Sumner, New Mexico, using JPL balloon-borne MkIV interferometer. Between 15 and 20 km, a significant fraction (20-60%) of the inorganic chlorine could not be accounted for by the sum of measured HCl, ClONO2, and HOCl. Laboratory measurements of the reaction of ClO radicals on sulfuric acid solutions have indicated that, along with HCl, small amounts of perchloric acid, HClO4, were formed. Very little is known about the fate of HClO4 in the stratosphere and we use a photochemical box model to determine the impact of this new species on the partitioning of inorganic chlorine in the stratosphere. Assuming that HClO4 is photochemically stable, it is shown that in the enhanced aerosol loading conditions resulting from Mt. Pinatubo's eruption, HClO4 could represent a significant reservoir of chlorine in the lower stratosphere, sequestering up to 0.2 ppbv (or 50%) of the total inorganic chlorine at 16 km. The occurrence of this new species could bring to closure the inorganic chlorine budget deficiency made apparent by recent ER-2 aircraft in situ measurements of HCl.

unmanned↗
NASA NTRS2001

In Situ Detection of OH, HO2, ClO, BrO, NO2, ClONO2, BrONO2, ClOOCl, H2O, and O3 from the ER2

We review here the scientific progress that has emerged during the period January 1, 1998 through March 31, 2001. Results from the Sage III Ozone Loss and Validation Experiment (SOLVE) and Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) mission, and continuing work on prior missions, taken in order, including radical control of ozone on the northern hemisphere stratosphere, evolution of NO2 over the arctic winter and its effects on reactive chlorine, and the first measurements of ClOOCl in the stratosphere.

Anderson, James G.↗
NASA NTRS2015

Fluorine and Lithium at the Kimberley Outcrop, Gale Crater

ChemCam is an active remote sensing instrument which has operated successfully on MSL since landing in August, 2012. Its laser pulses remove dust and to profile through weathering coatings of rocks up to 7 m away. Laser-induced breakdown spectroscopy (LIBS) produces emission spectra of materials ablated from the samples in electronically excited states. As the plasma cools, elements can recombine and molecular emission lines are observed. Recent experiments have shown that some of these molecular emissions can be much brighter than the associated atomic lines, especially when halo-gens and rare earth elements are present. We observed these molecular emissions in some of the ChemCam spectra and report the first detection of chlorine and fluorine with ChemCam. It is also the first time ever that fluorine has been detected on the surface of Mars. Among all the F-bearing observations, one third are observed in the Kimberley outcrop. We will dis-cuss the potential mineralogies related to these observations as well as the related elemental correlations and propose interpretations.

Forni, O.↗
NASA NTRS1978

Ozone profiles and chemical loss rates in the tropical stratosphere deduced from backscatter ultraviolet measurements

Analysis of data obtained by the backscatter ultraviolet (BUV) experiment on the Atmosphere Explorer E satellite has provided equatorial ozone mixing ratio profiles for equinox and solstice conditions. The combination of these results with a pure oxygen chemical model yields the rate of odd oxygen loss due to the sum of the odd hydrogen, nitrogen, and chlorine cycles. Use of recent mid-latitude stratospheric measurements of HO(x), NO(x), and ClO(x) with the BUV data provides an independent calculation of the catalytic loss. Below 45 km the agreement between the two sets of loss rates is satisfactory. At higher altitudes the odd hydrogen cycle provides far more O(x) loss than can be tolerated by the BUV measurements if the photodissociation of O2 is the only source and has the currently accepted magnitude. The results suggest either a tropical HO(x) concentration smaller than is now believed or the presence of a very large source of odd oxygen in the upper stratosphere and lower mesosphere.

Frederick, J. E.↗
NASA NTRS1986

Preliminary results of determination of chemical element concentrations in the aerosol of Venus clouds

An X-ray radiometeric experiment is described along with the results of measurements of the elemental composition of aerosols in Venusian clouds. A preliminary analysis of the data showed that sulfur is present in the range of heights 63 to 47 km with mean content of 5.8 mg/cu m and that chlorine is present in the height range 61 t0 52 km with a mean content of 4.1 mg/cu m. The results of measurements in the range 52 to 47 km may come to an agreement if phosphorus is present in the aerosol with a mean concentration of 7.7 mg/cu m.

Andreychikov, B. M.↗
NASA NTRS1996

Chlorine Deactivation in the Lower Stratospheric Polar Regions during late Winter: Results from UARS

Recovery from enhanced chlorine conditions in the lower stratospheric polar regions of both hemispheres is investigated using data from the Upper Atmosphere Research Satellite (UARS). Microwave Limb Sounder (MLS) measurements of ClO within the polar vortices are used to infer ClO(sub x) (ClO + 2Cl202) abundances that are then correlated with simultaneous Cryogenic Limb Array Etalon Spectrometer (CLAES) measurements of ClON02 and Halogen Occultation Experiment (HALOE) measurements of HCl obtained starting within 5 days of the end of the MLS and CLAES high-latitude observing periods in each hemisphere. Time series of vortex-averaged mixing ratios are calculated on two potential temperature surfaces (585 K and 465 K) in the lower stratosphere for approximately month-long intervals during late winter: August 17 - September 17, 1992, in the southern hemisphere and February 12 - March 16, 1993, in the northern hemisphere. The observed mixing ratios are adjusted for the effects of vertical transport using diabatic vertical velocities estimated from CLAES tracer data. In the northern hemisphere, the decrease in ClO, is balanced on both surfaces by an increase in ClON02- In the southern hemisphere, continuing polar stratospheric cloud activity prevents ClO from undergoing sustained decline until about September 3. In contrast to the northern hemisphere, there is no significant chemical change in vortex-averaged ClON02 at 465 K, and there is an apparent decrease in ClON02 at 585 K, even after the enhanced ClO abundances have started to recede. Results from the SLIMCAT chemical transport model initialized with UARS data and run with OH + ClO yields HCl + 02 as an 8% channel suggest that the primary recovery product in the south during this time period is not ClON02, but HCl. HALOE HCl mixing ratios are extrapolated back to the time of the MLS and CLAES data. At 585 K, the chlorine budget can be made to balance by extrapolating HCl back to a value of 0.6 parts per billion by volume (ppbv) at the beginning of the study period; at 465 K, the contribution from extrapolated HCl is not sufficient to offset the loss in ClOx, and there is a slight imbalance between the decrease in reactive chlorine and the change in chlorine reservoirs. The difficulty in closing the chlorine budget in the southern hemisphere may arise from complications caused by ongoing activation, incomplete photochemical assumptions, and/or inadequate data quality.

Santee, M. L.↗
NASA NTRS1993

Curved grating fabrication techniques for concentric-circle grating, surface-emitting semiconductor lasers

We describe the fabrication and operational characteristics of a novel, surface-emitting semiconductor laser that makes use of a concentric-circle grating to both define its resonant cavity and to provide surface emission. A properly fabricated circular grating causes the laser to operate in radially inward- and outward-going circular waves in the waveguide, thus, introducing the circular symmetry needed for the laser to emit a beam with a circular cross-section. The basic circular-grating-resonator concept can be implemented in any materials system; an AlGaAs/GaAs graded-index, separate confinement heterostructure (GRINSCH), single-quantum-well (SQW) semiconductor laser, grown by molecular beam epitaxy (MBE), was used for the experiments discussed here. Each concentric-circle grating was fabricated on the surface of the AlGaAs/GaAs semiconductor laser. The circular pattern was first defined by electron-beam (e-beam) lithography in a layer of polymethylmethacrylate (PMMA) and subsequently etched into the semiconductor surface using chemically-assisted (chlorine) ion-beam etching (CAIBE). We consider issues that affect the fabrication and quality of the gratings. These issues include grating design requirements, data representation of the grating pattern, and e-beam scan method. We provide examples of how these techniques can be implemented and their impact on the resulting laser performance. A comparison is made of the results obtained using two fundamentally different electron-beam writing systems. Circular gratings with period lambda = 0.25 microns and overall diameters ranging from 80 microns to 500 microns were fabricated. We also report our successful demonstration of an optically pumped, concentric-circle grating, semiconductor laser that emits a beam with a far-field divergence angle that is less than one degree. The emission spectrum is quite narrow (less than 0.1 nm) and is centered at wavelength lambda = 0.8175 microns.

Jordan, Rebecca H.↗
NASA NTRS2003

Advanced Global Atmospheric Gases Experiment (AGAGE): MIT Contribution

We describe in detail the instrumentation and calibrations used in the ALE, GAGE and AGAGE experiments and present a history of the majority of the anthropogenic ozone- depleting and climate-forcing gases in air based on these experiments. Beginning in 1978, these three successive automated high frequency in-situ experiments have documented the long-term behavior of the measured concentrations of these gases over the past twenty years, and show both the evolution of latitudinal gradients and the high frequency variability due to sources and circulation. We provide estimates of the long-term trends in total chlorine contained in long- lived halocarbons involved in ozone depletion. We summarize interpretations of these measurements using inverse methods to determine trace gas lifetimes and emissions. Finally, we provide a combined observational and modeled reconstruction of the evolution of chlorocarbons by latitude in the atmosphere over the past sixty years which can be used as boundary conditions for interpreting trapped air in glaciers and oceanic measurements of chlorocarbon tracers of the deep oceanic circulation. Some specific conclusions are: (a) International compliance with the Montreal Protocol is so far resulting in chlorofluorocarbon and chlorocarbon mole fractions comparable to target levels, (b) Mole fractions of total chlorine contained in long-lived halocarbons (CCl2F2, CCl3F, CH3CCl3, CCl4, CHClF2, CCl2FCClF2, CH3Cl, CH2Cl2, CHCl3, CCl2=CCl2) in the lower troposphere reached maximum values of about 3.6 ppb in 1993 and are beginning to slowly decrease in the global lower atmosphere, (c) The chlorofluorocarbons have atmospheric lifetimes consistent with destruction in the stratosphere being their principal removal mechanism, (d) Multi-annual variations in chlorofluorocarbon and chlorocarbon emissions deduced from ALUGAGWAGAGE data are consistent approximately with variations estimated independently from industrial production and sales data where available (CCl2F2 (CFC-12) and CCl2FCClF2 (CFC-113) show the greatest discrepancies), (e) The mole fractions of the hydrochlorofluorocarbons and hydrofluorocarbons, which are replacing the regulated halocarbons, are rising very rapidly in the atmosphere but, with the exception of the much longer manufactured CHClF2 (HCFC-22), they are not yet at levels sufficient to contribute significantly to atmospheric chlorine loading. These replacement species could in the future provide independent estimates of the global weighted-average OH concentration provided their industrial emissions are accurately documented, (f) In the future, analysis of pollution events measured using high frequency in-situ measurements of chlorofluorocarbons and their replacements may enable emission estimates at the regional level which, together with industrial end-use data, are of sufficient accuracy to be capable of identifying regional non-compliance with the Montreal Protocol.

Kurylo, Michael↗
NASA NTRS2014

Origin of Chlorobenzene Detected by the Curiosity Rover in Yellowknife Bay: Evidence for Martian Organics in the Sheepbed Mudstone?

The Sample Analysis at Mars (SAM) instrument on the Curiosity rover is designed to determine the inventory of organic and inorganic volatiles thermally evolved from solid samples using a combination of evolved gas analysis (EGA), gas chromatography mass spectrometry (GCMS), and tunable laser spectroscopy. The first solid samples analyzed by SAM, a scoop of windblown dust and sand at Rocknest (RN), revealed chlorinated hydrocarbons derived primarily from reactions between a martian oxychlorine phase (e.g. perchlorate) and terrestrial carbon from N-methyl-N-(tert-butyldimethylsilyl)-trifluoroacetamide (MTBSTFA) vapor present in the SAM instrument background. Chlorobenzene (CBZ) was also identified by SAM GCMS at RN at trace levels (approx.0.007 nmol) and was attributed to the reaction of chlorine with the Tenax polymers used in the hydrocarbon traps. After the RN analyses, Curiosity traveled to Yellowknife Bay and drilled two separate holes designated John Klein (JK) and Cumberland (CB). Analyses of JK and CB by both SAM and the CheMin x-ray diffraction instrument revealed a mudstone consisting of approx.20 wt% smectite clays, which on Earth are known to aid the concentration and preservation of organic matter. In addition, higher abundances and a more diverse suite of chlorinated hydrocarbons in CB compared to RN suggests that martian or meteoritic organic sources may be preserved in the mudstone. Here we discuss the SAM EGA and GCMS measurements of volatiles released from the Sheepbed mudstone. We focus primarily on the elevated CBZ detections at CB and laboratory analog experiments conducted to help determine if CBZ is derived from primarily terrestrial, martian, or a combination of sources.

origin of↗
NASA NTRS1994

Summer polar chemistry observations in the stratosphere made by HALOE

Regions of low stratospheric ozone that are anticorrelated with HCl, NO, and NO2 levels have been observed in the Arctic and Antarctic summers of 1992 and 1993 by the Halogen Occultation Experiment on the UARS platform. The low ozone areas are confined to the approximately 8-45 mb (approximately 33-21 km) region and poleward of approximately 60 deg in each hemisphere. While low polar summer ozone has been observed before, this is the first time simultaneous observations of relevant nitrogen and chlorine chemical species have been made. The phenomenon appears to be a recurring geophysical feature, and the satellite data should provide an excellent opportunity to improve our understanding of the chemistry causing these conditions.

Park, Jae H.↗
NASA NTRS1990

Particle chemistry impactor experiment

Polar stratospheric cloud (PSC) particles are collected on impactors and studied with regard to physical and chemical properties to help explain the importance of heterogeneous chemical reactions for stratospheric ozone depletion. The nitric, hydrochloric, and sulfuric acid content of stratospheric aerosol particles collected at 18 km altitude was determined. It is suggested that nitric acid is a component of polar stratospheric clouds. This is important for two reasons: (1) it proves that chlorine activation takes place at the surface of PSC particles by converting chemically inert chlorine nitrate to chlorine radicals that can react with ozone; and (2) if the PSC particles are large enough to settle out from the stratosphere, the possibility of nitric acid removal can result in the denitrification of the stratosphere.

Pueschel, R. F.↗
NASA NTRS2005

A Kinetic and Product Study of the Cl + HO2 Reaction

Absolute rate data and product branching ratios for the reactions Cl + HO2 to HCl + O2 (k1a) and Cl + HO2 to OH + ClO (k1b) have been measured from 226 to 336 K at a total pressure of 1 Torr of helium using the discharge flow resonance fluorescence technique coupled with infrared diode laser spectroscopy. For kinetic measurements, pseudo-first-order conditions were used with both reagents in excess in separate experiments. HO2 was produced by two methods: through the termolecular reaction of H atoms with O2 and also by the reaction of F atoms with H2O2. Cl atoms were produced by a microwave discharge of Cl2 in He. HO2 radicals were converted to OH radicals prior to detection by resonance fluorescence at 308 nm. Cl atoms were detected directly at 138 nm also by resonance fluorescence. Measurement of the consumption of HO2 in excess Cl yielded k1a and measurement of the consumption of Cl in excess HO2 yielded the total rate coefficient, k1. Values of k1a and k1 derived from kinetic experiments expressed in Arrhenius form are (1.6 +/- 0.2) x 10-11 exp[(249 +/- 34)/T] and (2.8 +/- 0.1) x 10-11 exp[(123 +/- 15)/T] cm3 molecule-1 s-1, respectively. As the expression for k1 is only weakly temperature dependent, we report a temperature-independent value of k1 = (4.5 +/- 0.4) x 10-11 cm3 molecule-1 s-1. Additionally, an Arrhenius expression for k1b can also be derived: k1b = (7.7 +/- 0.8) x 10-11 exp[-(708 +/- 29)/T] cm3 molecule-1 s-1. These expressions for k1a and k1b are valid for 226 K T 336 and 256 K T 296 K, respectively. The cited errors are at the level of a single standard deviation. For the product measurements, an excess of Cl was added to known concentrations of HO2 and the reaction was allowed to reach completion. HCl product concentrations were determined by IR absorption yielding the ratio k1a/k1 over the temperature range 236 K T 296 K. OH product concentrations were determined by resonance fluorescence giving rise to the ratio k1b/k1 over the temperature range 226 K T 336 K. Both of these ratios were subsequently converted to absolute numbers. Values of k1a and k1b from the product experiments expressed in Arrhenius form are (1.5 +/- 0.1) x 10-11 exp[(222 +/- 17)/T] and (10.6 +/- 1.5) x 10-11 exp[-(733 +/- 41)/T] cm3 molecule-1 s-1, respectively. These expressions for k1a and k1b are valid for 256 K T 296 and 226 K T 336 K, respectively. A combination of the kinetic and product data results in the following Arrhenius expressions for k1a and k1b of (1.4 +/- 0.3) x 10-11 exp[(269 +/- 58)/T] and (12.7 +/- 4.1) x 10-11 exp[-(801 +/- 94)/T] cm3 molecule-1 s-1, respectively. Numerical simulations were used to check for interferences from secondary chemistry in both the kinetic and product experiments and also to quantify the losses incurred during the conversion process HO2 to OH for detection purposes.

rate constants↗