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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

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NASA NTRS1991

Tests of stratospheric models - The reactions of atomic chlorine with O3 and CH4 at low temperature

The rate-constant ratio of the photochemical reactions of atomic chlorine with O3 and CH4 was determined using data from laboratory experiments on competitive chlorination of O3/CH4 mixtures at stratospheric temperatures (197-217 K). Two experimental approaches were used: (1) measuring the k1/k2 ratio for the reactions of atomic chlorine with ozone and methane and (2) testing for some of the ClO/CH3O2 chemistry. The chlorine and ozone concentrations were monitored by UV-Vis spectroscopy, and the CH3Cl concentration was measured by FTIR. The results on the k1/k2 ratio are in excellent agreement with the current NASA recommendation (DeMore et al., 1990), being only 12 percent higher. On the other hand, results on the ClO + CH3O2 reaction do not support the rate constant suggested by Simon et al. (1989).

Demore, W. B.↗

NASA NTRS1994

Application of Chlorine-Assisted Chemical Vapor Deposition of Diamond at Low Temperatures

Low temperature deposition of diamond has been achieved by a chlorine-assisted diamond chemical vapor deposition (CA-CVD) process. This method begins with the thermal dissociation of molecular chlorine into atomic chlorine in a resistively heated graphite furnace at temperatures between 1300 and 1500 deg. C. The atomic chlorine, upon mixing, subsequently reacts with molecular hydrogen and hydrocarbons. The rapid exchange reactions between the atomic chlorine, molecular hydrogen, and hydrocarbons give rise to the atomic hydrogen and carbon precursors required for diamond deposition. Homoepitaxial diamond growth on diamond substrates has been studied over the substrate temperature range of 100-950 C. It was found that the diamond growth rates are approximately 0.2 microns/hr in the temperature range between 102 and 300 C and that the growth rates do not decrease significantly with a decrease in substrate temperature. This is unique because the traditional diamond deposition using H2/CH4 systems usually disappears at substrate temperatures below approx. 500 deg. C. This opens up a possible route to the deposition of diamond on low-melting point materials such as aluminum and its alloys.

Pan, Chenyu↗

NASA NTRS1995

HCl Vapour Pressures and Reaction Probabilities for ClONO2 + HCl on Liquid H2SO4-HNO3-HCl-H20 Solutions

Henry's Law solubility constants for HCl have been measured for liquid H2SO4-HNO3-HCl-H2O solutions; the results are in good agreement with predictions from published semiempirical models. The ClONO2 + HCl reaction on the surfaces of such solutions with compositions simulating those of stratospheric aerosols has been investigated; as the composition changes following the temperature drop characteristic of the high-latitude stratosphere the reaction probability gamma increases rapidly. Furthermore, the gamma values remain essentially unchanged when HN03 uptake is neglected; the controlling factor appears to be the solubility of HCl. These results corroborate our earlier suggestion that supercooled liquid sulfate aerosols promote chlorine activation at low temperatures as efficiently as solid polar stratospheric cloud particles.

Elrod, M. J.↗

NASA NTRS1992

A molecular beam mass spectrometric study of the formation and photolysis of C(lc)lO dimer

A study of the chlorine oxides present at temperatures and pressures typical of the Antarctic stratosphere was carried out. A series of low temperature flow reactors was constructed and used in conjunction with molecular beam mass spectrometric techniques to identify species and characterize their kinetic behavior at temperatures of -20 to -70 C and pressures of from 30 to 130 Torr. It was found that the gas phase chlorine-oxygen system was quite complex at low temperatures. ClO dimer was identified and found to be thermodynamically very stable under stratospheric conditions. It was also found that any system which contained ClO also contained a larger oxide. The oxide was identified as Cl2O3. A survey of possible higher oxides, which have been postulated as possible chlorine sinks in the stratosphere, was also carried out. The rate of formation of ClO dimer was measured as a function of temperature and pressure. Measurements were made of both the decay of ClO and the formation of the dimer. By comparing these rates it was determined that virtually all of the ClO was converted to the dimer under stratospheric conditions, and that the other ClO reactions were not important under these conditions.

Greene, Frank T.↗

NASA NTRS2021

Martian subsurface cryosalt expansion and collapse as trigger for landslides

On Mars, seasonal martian flow features known as recurring slope lineae (RSL) are prevalent on sun-facing slopes and are associated with salts. On Earth, subsurface interactions of gypsum with chlorides and oxychlorine salts wreak havoc: instigating sinkholes, cave collapse, debris flows, and upheave. Here, we illustrate (i) the disruptive potential of sulfate-chloride reactions in laboratory soil crust experiments, (ii) the formation of thin films of mixed ice-liquid water “slush” at −40° to −20°C on salty Mars analog grains, (iii) how mixtures of sulfates and chlorine salts affect their solubilities in low-temperature environments, and (iv) how these salt brines could be contributing to RSL formation on Mars. Our results demonstrate that interactions of sulfates and chlorine salts in fine-grained soils on Mars could absorb water, expand, deliquesce, cause subsidence, form crusts, disrupt surfaces, and ultimately produce landslides after dust loading on these unstable surfaces.

J. L. Bishop↗

NASA NTRS1988

Chemistry of the CO dimer at low temperatures

Researchers conducted a series of experiments on the chlorine-catalyzed photodecomposition of O sub 3 both in the gas and in inert solvents such as CF sub 4 and CO sub 2 in the temperature range about 190 to 225 K. The liquid medium was chosen in order to minimize possible surface loss of long-lived ClO dimer, and to aid in the stabilization of transient excited intermediates. The mechanism of dimer formation was as follows: (1) Cl sub 2 + hv yields Cl + Cl; (2) Cl + O sub 3 yields ClO + O sub 2; (3) ClO + ClO yields Cl sub 2 O sub 2. The experiments were done in cooled low temperature cells, with irradiation from an Osram high pressure mercury arc, filtered to remove radiation below 325 nm. Spectral analysis was by means of a Cary Model 2200 UV spectrometer. The principal objectives were: (1) to determine the lifetime of the dimer as a function of temperature; (2) to observe spectral changes in the mixtures which could be attributed to dimer or related products; and (3) to observe chemical or photochemical reactions of the dimer.

Demore, W. B.↗

NASA NTRS1983

Hydrodesulfurization of chlorinized coal

A method of desulfurization is described in which high sulfur coals are desulfurized by low temperature chlorinolysis of coal in liquid media, preferably water, followed by hydrodesulfurization at a temperature above 500 C. The coals are desulfurized to an extent of up to 90% by weight and simultaneously dechlorinated to a chlorine content below 0.1% by weight. The product coals have lower volatiles loss, lower oxygen and nitrogen content and higher fixed carbon than raw coals treated with hydrogen under the same conditions. Heating the chlorinated coal to a temperature above 500 C. in inert gas such as nitrogen results in significantly less desulfurization.

Kalvinskas, J. J.↗

NASA NTRS2005

Uptake of Hypobromous Acid (HOBr) by Aqueous Sulfuric Acid Solutions: Low-Temperature Solubility and Reaction

Hypobromous acid (HOBr) is a key species linking inorganic bromine to the chlorine and odd hydrogen chemical families. We have measured the solubility of HOBr in 45 - 70 wt% sulfuric acid solutions representative of upper tropospheric and lower stratospheric aerosol composition. Over the temperature range 201 - 252 K, HOBr is quite soluble in sulfuric acid, with an effective Henry's law coefficient, H* = 10(exp 4) - 10(exp 7) mol/L/atm. H* is inversely dependent on temperature, with Delta H = -46.2 kJ/mol and Delta S = -106.2 J/mol/K for 55 - 70 wt% H2SO4 solutions. Our study includes temperatures which overlap both previous measurements of HOBr solubility. For uptake into aqueous 45 wt% H2SO4, the solubility can be described by log H* = 3665/T - 10.63. For 55 - 70 wt% H2SO4, log H* = 2412/T - 5.55. At temperatures colder than approx. 213 K, the solubility of HOBr in 45 wt% H2SO4 is noticeably larger than in 70 wt% H2SO4. The solubility of HOBr is comparable to that of HBr, indicating that upper tropospheric and lower stratospheric aerosols should contain equilibrium concentrations of HOBr which equal or exceed those of HBr. Our measurements indicate chemical reaction of HOBr upon uptake into aqueous sulfuric acid in the presence of other brominated gases followed by evolution of gaseous products including Br2O and Br2, particularly at 70 wt% H2SO4.

Iraci, Laura T.↗

NASA NTRS1982

Coal desulfurization by aqueous chlorination

A method of desulfurizing coal is described in which chlorine gas is bubbled through an aqueous slurry of coal at low temperature below 130 degrees C., and at ambient pressure. Chlorinolysis converts both inorganic and organic sulfur components of coal into water soluble compounds which enter the aqueous suspending media. The media is separated after chlorinolysis and the coal dechlorinated at a temperature of from 300 C to 500 C to form a non-caking, low-sulfur coal product.

Kalvinskas, J. J.↗

NASA NTRS1988

Stability and photochemistry of ClO dimers formed at low temperature in the gas phase

The recent observations of elevated concentrations of the ClO radical in the austral spring over Antarctica have implicated catalytic destruction by chlorine in the large depletions seen in the total ozone column. One of the chemical theories consistent with an elevated concentration of the ClO is a cycle involving the formation of the ClO dimer through the association reaction: ClO + ClO = Cl2O2 and the photolysis of the dimer to give the active Cl species necessary for O3 depletion. Here, researchers report experimental studies designed to characterize the dimer of ClO formed by the association reaction at low temperatures. ClO was produced by static photolysis of several different precursor systems: Cl sub 2 + O sub 3; Cl sub 2 O sub 2; OClO + Cl sub 2 O spectroscopy in the U.V. region, which allowed the time dependence of Cl sub 2, Cl sub 2 O, ClO, OClO, O sub 3 and other absorbing molecules to be determined.

Cox, R. A.↗

NASA NTRS1985

Effect of chloride incorporation on the crystallization of zirconium-barium-lanthanum-aluminum fluoride glass

One aspect of the influence of preparation procedure on the crystallization behavior of a zirconium-barium-lanthanum-aluminum fluoride glass was studied. The crystallization pattern of this glass may be affected by the chlorine concentration within it. In particular, when such glasses are heated at low temperatures, the alpha-Ba-Zr-F6 crystalline phase forms only in those glasses which contain chloride.

Neilson, G. F.↗

NASA NTRS1995

Interannual Variability of the North Polar Vortex in the Lower Stratosphere During the UARS Mission

Three of the four northern winters since the launch of the Upper Atmosphere Research Satellite (UARS) had daily NMC minimum temperatures in the lower stratosphere that approached or fell below the lowest values experienced during the previous 13 years. These low temperatures were more conducive to formation of polar stratospheric clouds and thus to associated chlorine activation and associated chemical loss of ozone in the lower stratosphere.

North↗

NASA NTRS1998

Ozone Depletion at Mid-Latitudes: Coupling of Volcanic Aerosols and Temperature Variability to Anthropogenic Chlorine

Satellite observations of total ozone at 40-60 deg N are presented from a variety of instruments over the time period 1979-1997. These reveal record low values in 1992-3 (after Pinatubo) followed by partial but incomplete recovery. The largest post-Pinatubo reductions and longer-term trends occur in spring, providing a critical test for chemical theories of ozone depletion. The observations are shown to be consistent with current understanding of the chemistry of ozone depletion when changes in reactive chlorine and stratospheric aerosol abundances are considered along with estimates of wave-driven fluctuations in stratospheric temperatures derived from global temperature analyses. Temperature fluctuations are shown to make significant contributions to model calculated northern mid-latitude ozone depletion due to heterogeneous chlorine activation on liquid sulfate aerosols at temperatures near 200-210 K (depending upon water vapor pressure), particularly after major volcanic eruptions. Future mid-latitude ozone recovery will hence depend not only on chlorine recovery but also on temperature trends and/or variability, volcanic activity, and any trends in stratospheric sulfate aerosol.

Solomon, S.↗

NASA NTRS1986

Shock-tube pyrolysis of chlorinated hydrocarbons - Formation of soot

Soot formation in pyrolysis of chlorinated methanes, their mixtures with methane, and chlorinated ethylenes were studied behind reflected shock waves by monitoring the attenuation of an He-Ne laser beam. An additional single-pulse shock-tube study was conducted for the pyrolysis of methane, methyl chloride, and dichloromethane. The experiments were performed at temperatures 1300-3000 K, pressures of 0.4-3.6 bar, and total carbon atom concentrations of 1-5 x 10 to the 17th atoms cu cm. The amounts of soot produced in the pyrolysis of chlorinated hydrocarbons are larger than that of their nonchlorinated counterparts. The sooting behavior and product distribution can be generally explained in terms of chlorine-catalyzed chemical reaction mechanisms. The pathway to soot from chlorinated methanes and ethylenes with high H:Cl ratio proceeds via the formation of C2H, C2H2, and C2H3 species. For chlorinated hydrocarbons with low H:Cl ratio, the formation of C2 and its contribution to soot formation at high temperatures becomes significant. There is evidence for the importance of CHCl radical and its reactions in the pyrolysis of dichloromethane.

Frenklach, M.↗

NASA NTRS1973

Batteries for storage of wind-generated energy

Cost effectiveness characteristics of conventional-, metal gas-, and high energy alkali metal-batteries for wind generated energy storage are considered. A lead-acid battery with a power density of 20 to 30 watt/hours per pound is good for about 1500 charge-discharge cycles at a cost of about $80 per kilowatt hour. A zinc-chlorine battery that stores chlorine as solid chlorine hydrate at temperatures below 10 C eliminates the need to handle gaseous chlorine; its raw material cost are low and inexpensive carbon can be used for the chlorine electrode. This system has the best chance to replace lead-acid. Exotic alkali metal batteries are deemed too costly at the present stage of development.

Schwartz, H. J.↗

NASA NTRS1990

Equilibrium constant for the reversible reaction ClO + O2 - ClO-O2

It is shown here that the equilibrium constant for the reversible reaction ClO + O2 - ClO-O2 at stratospheric temperatures must be at least three orders of magnitude less than the current NASA upper limit. The new upper limit greatly diminishes the possible role of ClO-O2 in the chlorine-photosensitized decomposition of O3. Nevertheless, it does not preclude the possibility that it is a significant reservoir of ClO, as well as a possible reactant, at low temperatures characteristic of polar vortices.

Demore, W. B.↗

NASA NTRS2019

Perchlorate on Mars - Overview and Implications

Perchlorate was first detected on Mars by the Wet Chemistry Laboratory (WCL) instrument on the Phoenix lander at a concentration of ~0.5 wt% in northern plains soils. Since that initial detection, perchlorate (and likely chlorate) have been detected on Mars by both surface and orbital instruments. Perchlorate (ClO4-) is an oxidized chlorine compound and salts of perchlorate are kinetically stable (though very reactive at high temperature), very soluble, deliquescent, and have low eutectic temperature (which decreases the temperature for stable liquids on Mars). Chlorate (ClO3-) salts are similar, though they are less kinetically stable than perchlorates. Because many of the analytical signatures of perchlorate and chlorate are similar to the instruments we have used on Mars, we cannot always determine which species is present, so we will use the more generic term “oxychlorine” when referring to perchlorate and/or chlorate.

Archer, P. D.↗

NASA NTRS1981

Coal desulfurization by low temperature chlorinolysis, phase 3

Laboratory scale, bench scale batch reactor, and minipilot plant tests were conducted on 22 bituminous, subbituminous, and lignite coals. Chemical pretreatment and post treatment of coals relative to the chlorination were tried as a means of enhancing desulfurization by the chlorinolysis process. Elevated temperature (500-700 C) hydrogen treatment of chlorinolysis-processed coal at atmospheric pressure was found to substantially increase coal desulfurization up to 90 percent. Sulfur forms, proximate and ultimate analyses of the processed coal are included. Minipilot plant operation indicates that the continuous flow reactor provides coal desulfurization results comparable to those obtained in the batch reactor. Seven runs were conducted at coal feed rates of 1.5 to 8.8 kg per hour using water and methylchloroform solvents, gaseous chlorine feed of 3 to 31.4 SCFH at 21 to 70 C, and atmospheric pressure for retention times of 20 to 120 minutes.

Kalvinskas, J. J.↗