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At least 127 records · Page 7

Test results of JPL LiSOCl sub 2 cells

In the development of high rate Li-SO-Cl2 cells for various applications, the goal is to achieve 300 watt-hours per kilogram at the C/2 (5 amp) rate in a D cell configuration. The JPL role is to develop the understanding of the performance, life, and safety limiting characteristics in the cell and to transfer the technology to a manufacturer to produce a safe, high quality product in a reproducible manner. The approach taken to achieve the goals is divided into four subject areas: cathode processes and characteristics; chemical reactions and safety; cell design and assembly; and performance and abuse testing. The progress made in each of these areas is discussed.

Halpert, G.↗

A kinetics study of the homogeneous and heterogeneous components of the HCl + ClONO2 reaction

The kinetics of the reaction HCl + ClONO2 to Cl2 + HNO3 were investigated at 298 K using a flow reactor with FTIR analysis to assess the importance of this reaction for stratospheric chemistry. The observed reaction was characteristic of a heterogeneous process; an upper limit of 5 x 10 to the -18th cu cm/molecule per s was obtained for the homogeneous gas phase rate constant. From calculations of the first order wall rate constant, estimates were made of the reaction rate on stratospheric aerosols. Because both HCl and ClONO2 need to be adsorbed on the particle surface, the reaction will be of negligible importance under most stratospheric conditions.

Friedl, Randall R.↗

Reaction of chlorine nitrate with hydrogen chloride and water at Antarctic stratospheric temperatures

Laboratory studies of heterogeneous reactions important for ozone depletion over Antarctica are reported. The reaction of chlorine nitrate (ClONO2) with H2O and HCl on surfacers that simulate polar stratospheric clouds are studied at temperatures relevant to the Antarctic stratosphere. The gaseous products of the resulting reactions, HOCl, Cl2O, and Cl2, could readily photolyze in the Antarctic spring to produce active chlorine for ozone depletion. Furthermore, the additional formation of condensed-phase HNO3 could serve as a sink for odd nitrogen species that would otherwise scavenge the active chlorine.

Tolbert, Margaret A.↗

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.↗

Production and characterization of CdCl2 intercalated graphite fibers

Graphite fibers were intercalated using CdCl2 as a Cl source and Cl2 as carrier gas. Fibers were synthesized with a resistivity-density figure of merit comparable to that of copper. These fibers can withstand practical electrical current densities as high as 54,000 A/sq cm. Their thermal coefficient of resistivity is 0.0016 C, which is approximately 41 percent of those for copper and aluminum.

Gooden, Clarence E.↗

Heterogeneous chemistry related to Antarctic ozone depletion: Reaction of ClONO2 and N2O5 on ice surfaces

Laboratory studies of heterogeneous reactions of possible importance for Antarctic ozone depletion were performed. In particular, the reactions of chlorine nitrate (ClONO2) and dinitrogen pentoxide (N2O5) were investigated on ice and HCl/ice surfaces. These reactions occur on the surfaces of polar stratospheric clouds (PSCs) over Antarctica. One reaction transforms the stable chlorine reservoir species (ClONO2 and HCl) into photochemically active chlorine in the form of HOCl and Cl2. Condensation of HNO3 in the reactions removes odd nitrogen from the stratosphere, a requirement in nearly all models of Antarctic ozone depletion. Other reactions may also be important for Antarctic ozone depletion. Like the reactions of chlorine nitrate, these reactions deplete odd nitrogen through HNO3 condensation. In addition, one reaction converts a stable chlorine reservior species (HCl) into photochemically active chlorine (ClNO2). These reactions were studied with a modified version of a Knudsen cell flow reactor.

Tolbert, Margaret A.↗

Mixing ratios of trace gases in the austral polar atmosphere during August and September of 1987

Mixing ratios are presented for a number of long-lived trace gases in the austral polar atmosphere during August and September of 1987. The recent discovery of a 12-year trend of increasing depletion of ozone over the Antarctic Continent in the spring of each year led to numerous theoretical interpretations and several scientific expeditions to the region. The results herein were obtained as part of a major effort involving penetration of the region of ozone depletion by NASA's multi-instrumented aircraft. One of the 14 instruments on the high-altitude ER-2 aircraft collected pressurized air samples between latitudes of 53 degrees and 72 degrees south at pressure altitudes up to 21 km in a series of 12 flights from Punta Arenas, Chile, over the Palmer Peninsula. The sampling system, located in the nose section of ER-2, has an inlet tube in the free airstream, a metal-bellows air pump, and 14 specially treated 1.6 l stainless-steel canisters for containing the pressurized air at 350 kPa. A typical flight profile consisted of a southbound path on the 428 K potential temperature surface, a descent to a pressure altitude of 13.7 km, a climb to the 460 K surface, and return on this surface. Mixing ratios for the trace gases were obtained from gas chromatographic analyses of the pressurized air samples. Of the species measured, the mixing ratios for CH4, CO, N2O, CF2 Cl2, CFCl3, CH3, CCl3, CCl4, and C2F3Cl3 are reported here.

Vedder, James F.↗

Studies of ClO and BrO reactions important in the polar stratosphere: Kinetics and mechanism of the ClO+BrO and ClO+ClO reactions

The reactions, BrO + ClO yields Br + ClOO (1a) yields Br + OClO (1b) yields BrCl + O2 (1c) and ClO + ClO yields Cl + CiOO (2a) yields Cl + OClO (2b) yields Cl2 + O2 (2c) yields (ClO)2 (2d) have assumed new importance in explaining the unusual springtime depletion of ozone observed in the Antarctic stratosphere. The mechanisms of these reactions involve the formation of metastable intermediates which subsequently decompose through several energetically allowed products providing the motivation to study these reactions using both the discharge flow-mass spectrometric and flash photolysis - ultraviolet absorption techniques. These methods have also been used to explore aspects of the kinetics and spectroscopy of the ClO dimer.

Friedl, Randall R.↗

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.↗

Model gases for the detailed study of microscopic chemical nonequilibrium in diatomic gas flows

It is shown that chlorine (Cl2) and iodine (I2) are suitable model diatomic gases to use in theoretical studies of chemical nonequilibrium that account for rotational and vibrational as well as electronic processes in a gas. Because of the low temperature at which significant dissociation can be achieved in iodine, it is a particularly attractive candidate for the study of relatively low temperature chemically reacting flows, permitting detailed knowledge of the nonequilibrium populations of translational, rotational, vibrational and electronic energy levels. A preliminary investigation indicates that a useful iodine flow facility can be constructed and that diagnostic techniques are available to validate in detail prediction techniques for nonequilibrium flows.

Kunc, Joseph A.↗

Oxygen production processes on the Moon: An overview

The production of oxygen on the Moon utilizing indigenous material is paramount to a successful lunar colonization. Several processes were put forth to accomplish this. The lunar liquid oxygen (LLOX) generation schemes which have received the most study to date are those involving: (1) the reduction of ilmenite (FeTiO3) by H2, C, CO, CH4, CO-Cl2 plasma; (2) magma electrolysis, both unadulterated and fluoride-fluxed, and (3) several others, including carbo-chlorination, HF acid leaching, fluorine extraction, magma oxidation, and vapor pyrolysis. The H2 reduction of ilmenite and magma electrolysis processes have received the most study to date. At this stage of development, they both appear feasible schemes with various pros and cons. However, all processes should be addressed at least at the onset of the considerations. It is ultimatley the energy requirements of the entire process, including the acquisition of feedstock, which will determine the mode of oxygen productions. There is an obvious need for considerably more experimentation and study. Some of these requisite studies are in progress, and several of the most studied and feasible processes for winning oxygen from lunar materials are reviewed.

Taylor, Lawrence A.↗

Annular denuder systems: Precision and applicability to stratospheric sampling

Annular denuder systems (ADS) are designed to sample both gases and particles from ambient air without cross interference. The ADS's were used to detect chemical gradients over rural forest canopies. Accurate and precise methods for the sampling and analysis of low concentrations of gaseous and particulate species over short sampling periods were developed. Typical analytical precision data for nitrate and sulfate are shown. Both sampling and analytical precision data for a 2 hour test using four collocated ADS's are presented. On this particular day, the overall precision for HNO3 was unusually poor. The overall precision for the major constituents of interest is generally about 3 to 5 percent for typical ambient concentrations. The ADS's could potentially be used to determine the concentrations of HNO3 and fine-particle nitrate in the stratosphere, and to simultaneously characterize the chemical composition of stratospheric aerosols. Assuming 50 mb pressure, a 2 hour sampling time, a 50 Lpm sampling rate, and a low blank value, an overal precision of about 15 percent should be possible for 1 ppbv of HNO3 or nitrate, which would include nitric-acid trihydrate (NAT); and pump-driven systems could accommodate more complex systems involving denuders and filter packs in sequence. Alternate coatings could possibly be developed to selectively sample species such as Cl2 and ClNO3. The ADS's might also be useful in laboratory studies of heterogeneous chemical reactions involving NAT aerosols.

Randtke, Stephen J.↗

Thermodynamic models of the chemistry of lunar volcanic gases

Thermodynamic models and mass-balance arguments are used to constrain the chemistry of lunar volcanic gases. The results predict that lunar gases were dominated by reduced C and S gases such as CO, COS, CS2, S2. The more oxidized gases CO2 and SO2 were also important, but only in limited temperature ranges. Gases such as Cl2, CCl4, and CF4 were more abundant than HF and HCl, which were the two major H compounds in the lunar gases. Chlorides and fluorides were important species for transporting many volatile and ore-forming metals, and the implications for fractionating and concentrating metals into lunar ore-deposits merit further study.

Fegley, Bruce, Jr.↗

Heterogeneous reactions of chlorine nitrate and hydrogen chloride on type I polar stratospheric clouds

A fast-flow reactor coupled with a quadrupole mass spectrometer was used to study the heterogeneous reactions ClONO2 + HCl yields Cl2 + HNO3 (1) and ClONO2 + H2O yields HOCl + HNO3 (2) on vapor-deposited HNO3-H2O ice substrates. It was found that the sticking coefficient of HCl on these substrates was a strong function of the substrate composition, ranging from about 2 x 10 exp -5 at nitric acid trihydrate composition to 6 x 10 exp -3 at 45 wt pct HNO3. The HNO3-H2O ice substrates were found to have large internal surface areas, and corrections for gas-phase diffusion within the porous ices were applied to observed loss rates.

Leu, Ming-Taun↗

Investigation of etching techniques for superconductive Nb/Al-Al2O3/Nb fabrication processes

Wet etching, CF4 and SF6 reactive ion etching (RIE), RIE/wet hybrid etching, Cl-based RIE, ion milling, and liftoff techniques have been investigated for use in superconductive Nb/Al-Al2O3/Nb fabrication processes. High-quality superconductor-insulator-superconductor (SIS) junctions have been fabricated using a variety of these etching methods; however, each technique offers distinct tradeoffs for a given process an wafer design. In particular, it was shown that SF6 provides an excellent RIE chemistry for low-voltage anisotropic etching of Nb with high selectivity to Al. The SF6 tool has greatly improved the trilevel resist junction insulation process. Excellent repeatability, selectivity with respect to quartz, and submicron resolution make Cl2 + BCl3 + CHCl3 RIE a very attractive process for trilayer patterning.

Lichtenberger, A. W.↗

Particulate multi-phase flowfield analysis for advanced solid rocket motor

Particulate multi-phase flowfield with chemical reaction for a 2D advanced solid rocket motor (ASRM) is analyzed using the finite difference Navier-Stokes (FDNS) code. The flowfield in the aft dome cavity of the ASRM is examined and its significant impact on the motor operation and performance is demonstrated. Chemical reaction analysis is performed for H2O, O2, H2, O, H, OH, CO, CO2, Cl, Cl2, HCl, and N2. The turbulent dispersion effect is calculated with the Monte Carlo method. Result show that a recirculation zone exists at the entry of the aft-dome cavity. The particle impingement could cause the erosion and damage nozzle wall. Accumulating in the impingement area the particles change the wall shape and affect the motor performance.

Liaw, Paul↗

Magmatic volatiles and the weathering of Mars

The sources for volatiles on Mars have been the subject of many hypotheses for exogenous influences including late accretion of volatile-enriched material, impact devolatilization to create massive early atmospheres, and even major bombardment by comets. However, the inventory of chemically active volatiles observable at the contemporary surface of Mars is consistent with domination by endogenous, subsequent planetary processes, viz., persistent magmatic outgassing. Volcanism on Mars has been widespread in both space and time. Notwithstanding important specific differences between the mantles of Earth and Mars, the geochemical similarities are such that the suite of gases emitted from Martian volcanic activity should include H2O, CO2, S-containing gases (e.g. H2S and/or SO2), and Cl-containing gases (e.g., Cl2 and/or HCl). H2O and CO2 exist in the atmosphere of Mars. Both are also present as surface condensates. However, spectroscopic observations of the Martian atmosphere clearly show that the S- and Cl-containing gases are severely depleted, with upper limits of less than or equal to 10(exp -7) the abundance of CO2. Likewise, there is no evidence of polar condensates of compounds of these elements as there is for CO2 and H2O. Within the soil, on the other hand, there has been direct measurement of incorporated H2O and abundant compounds containing S and Cl. Barring some as yet implausible geochemical sequestering process, the S/Cl ratio of about 6:1 in Martian soils implies a limit of 5% on the contribution of matter of solarlike composition (e.g., carbonaceous chondrite or cometary material) to these volatiles. Hence, exogenous sources are minor or not yet observed. From analysis of elemental trends in Martian soils, it has been recently shown that a simple two-component model can satisfy the Viking in situ measurements. Component A includes Si and most or all the Al, Ca, Ti, and Fe. Component B, taken as 16 +/- 3% by weight of the total, contains S and most or all the Cl and Mg. These results constrain several models of Martian soil mineralogy but are consistent with a mixture of silicates (such as Fe-rich clays and accessory minerals and soluble salts). The overall element profile is notably like shergottites, with significant incorporation of chemically reactive atmospheric gases from magmatic degassing.

Clark, B. C.↗

Chlorine chemistry on polar stratospheric cloud particles in the Arctic winter

Simultaneous in situ measurements of hydrochloric acid (HCl) and chlorine monoxide (ClO) in the Arctic winter vortex showed large HCl losses of up to 1 ppbv, which were correlated with high ClO levels of up to 1.4 ppbv. Air parcel trajectory analysis identified that this conversion of inorganic chlorine occurred at air temperatures of less than 196 -/+ 4 kelvin. High ClO was always accompanied by loss of HCl mixing ratios equal to 1/2(ClO+ 2Cl2O2). These data indicate that the heterogeneous reaction HCl + ClONO2 - Cl2 + HNO3 on particles of polar stratospheric clouds establishes the chlorine partitioning, which, contrary to earlier notions, begins with an excess of ClONO2, not HCl.

Webster, C. R.↗