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At least 91 records · Page 5

Chlorination processing of local planetary ores for oxygen and metallurgically important metals

The use of chlorine to extract, reclaim, and purify metals has attractive possibilities for extraterrestrial processing of local planetary resources. While a complete cyclic process has been proposed for the recovery of metallurgically significant metals and oxygen, herein the chlorination step of the cycle is examined. An experimental apparatus for reacting refractory materials, such as ilmenite, in a microwave induced plasma is being built. Complex equilibria calculations reveal that stable refractory materials can, under the influence of a plasma, undergo chlorination and yield oxygen as a by-product. These issues and the potential advantages for plasma processing in space are reviewed. Also presented is a discussion of the complex equilibria program used in the analysis.

Lynch, D. 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.↗

Arctic chlorine monoxide observations during spring 1993 over Thule, Greenland, and implications for ozone depletion

We have determined the vertical distribution of chlorine monoxide (ClO), from measurements of pressure-broadened molecular-emission spectra made over Thule, Greenland, during the 1993 Arctic spring. The measurements show a weak lower stratospheric layer of chlorine monoxide inside the vortex in late February, which was, however, significantly greater in mixing ratio than that seen in observations we made in the spring of 1992. ClO was also observed in much smaller quantities in early to mid-March 1993 when Thule was outside the vortex. The amount of ClO within the vortex was severely reduced by the time it returned over Thule in late March. This reduction occurred several weeks earlier relative to the winter solstice than the decline of ClO inside the Antarctic vortex in 1993. The enhanced Arctic lower stratospheric layer seen in late February 1993 at a nearly equivalent photochemical period, and beyond. We have calculated daily ozone loss rates, due primarily to the dimer chlorine catalytic cycle, from both sets of measurements. The vertical integral of the Arctic daily percentage ozone loss when the largest ClO levels were present, at the end of February, is found to be approximately one quarter of that in the Antarctic at a photochemical period only 1 week later. The relative weakness of daily ozone depletion, combined with the early disappearance of ClO in the Arctic, suggests that hemispheric dilution by ozone-poor air from within the Arctic vortex is unlikely to be sufficient to explain the historically extreme loss of midlatitude northern hemisphere ozone which began in 1992 and persisted throughout 1993.

Shindell, D. T.↗

Increase in Levels of Stratospheric Chlorine and Fluorine Loading between 1985 and 1992

Mixing ratios of 3.44 ppbv (parts per billion by volume) and 1.23 ppbv for HCl and HF above 50 km, surrogates for total chlorine and fluorine, have been measured by the Atmospheric Trace Molecule Spectroscopy (ATMOS) experiment on a March 1992 flight of the Space Shuttle. Compared to the measured values obtained on a 1985 flight, these correspond to a 37% and 62% increase for HCl and HF, respectively. The derived trend in HCl (approx. 0.13 ppbv per year) is in good agreement with the model-predicted increase in chlorine loading of 0.13 ppbv per year, and with the measured trends in HCl total column abundance from reported ground-based observations. The main source of this change can be attributed to the release of man-made chlorofluorocarbons (CFC's) and hydro-chloro-fluoro-carbons (HCFC's). This new value for HCl represents an upper limit to the inorganic chlorine concentration in the stratosphere available for participation in photochemical processes which destroy ozone.

Gunson, M. R.↗

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.↗

Inorganic Chlorine Partitioning in the Summer Lower Stratosphere: Modeled and Measured [ClONO2/HCl] During POLARIS

We examine inorganic chlorine (Cly) partitioning in the summer lower stratosphere using in situ ER-2 aircraft observations made during the Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) campaign. New steady state and numerical models estimate [ClONO2]/[HCl] using currently accepted photochemistry. These models are tightly constrained by observations with OH (parameterized as a function of solar zenith angle) substituting for modeled HO2 chemistry. We find that inorganic chlorine photochemistry alone overestimates observed [ClONO2]/[HCl] by approximately 55-60% at mid and high latitudes. On the basis of POLARIS studies of the inorganic chlorine budget, [ClO]/[ClONO2], and an intercomparison with balloon observations, the most direct explanation for the model-measurement discrepancy in Cly partitioning is an error in the reactions, rate constants, and measured species concentrations linking HCl and ClO (simulated [ClO]/[HCl] too high) in combination with a possible systematic error in the ER-2 ClONO2 measurement (too low). The high precision of our simulation (+/-15% 1-sigma for [ClONO2]/[HCl], which is compared with observations) increases confidence in the observations, photolysis calculations, and laboratory rate constants. These results, along with other findings, should lead to improvements in both the accuracy and precision of stratospheric photochemical models.

Voss, P. B.↗

A New Formulation of Equivalent Effective Stratospheric Chlorine (EESC)

Equivalent effective stratospheric chlorine (EESC) is a convenient parameter to quantify the effects of halogens (chlorine and bromine) on ozone depletion in the stratosphere. We show and discuss a new formulation of EESC that now includes the effects of age-of-air dependent fractional release values and an age-of-air spectrum. This new formulation provides quantitative estimates of EESC that can be directly related to inorganic chlorine and bromine throughout the stratosphere. Using this EESC formulation, we estimate that human-produced ozone depleting substances will recover to 1980 levels in 2041 in the midlatitudes, and 2067 over Antarctica. These recovery dates are based upon the assumption that the international agreements for regulating ozone-depleting substances are adhered to. In addition to recovery dates, we also estimate the uncertainties in the estimated time of recovery. The midlatitude recovery of 2041 has a 95% confidence uncertainty from 2028 to 2049, while the 2067 Antarctic recovery has a 95% confidence uncertainty from 2056 to 2078. The principal uncertainties are from the estimated mean age-of-air, and the assumption that the mean age-of-air and fractional release values are time independent. Using other model estimates of age decrease due to climate change, we estimate that midlatitude recovery may be accelerated from 2041 to 2031.

Newman, P. A.↗

Lethality is Local, but Survival is Systemic: Temporal and Multi-Organ Responses to Chlorine Gas Exposure in a Murine Model

Chlorine gas (Cl2) is a highly toxic chemical associated with both localized lung injury and systemic health effects. While pulmonary damage has been well characterized, the systemic inflammatory and metabolic responses remain poorly understood. We aimed to define the temporal and multi-organ responses to Cl2 exposure in a murine model, with a focus on identifying spatiotemporal inflammation and its impact on survival and lethality. SKH1 mice were exposed for 10 min to varying concentrations of Cl2 (94.4–810 ppm, representative of non-lethal, LD10, and LD50 doses) and monitored for respiratory function, perfusion, and acidosis using organ-specific imaging. At multiple time points (40 min, 6 h, 24 h, and 7 d), we measured phosphoproteins, cytokines, chemokines, growth factors, and metabolic hormones in the lungs, heart, cortex, and plasma. Statistical modeling and logistic regression were used to identify biomarkers associated with lethality and survival. We found that lung injury was the primary cause of potential lethality, particularly via early phosphoprotein signaling disruptions. However, survival correlated with early systemic coordination of inflammatory and metabolic signals across organs. Perfusion and acidosis imaging were strongly associated with chemokine and hormone responses. Key survival-associated plasma biomarkers included decreased insulin, increased ghrelin, and decreased eotaxin. While potential lethality from Cl2 exposure is locally driven by pulmonary injury, survival depends on systemic, multi-organ responses that occur rapidly post-exposure. Within this model, our findings identify a potential therapeutic window to enhance survival and suggest candidate biomarkers that may be explored translationally for both triage and treatment of chlorine-related incidents.

chlorine gas↗

UARS Microwave Limb Sounder Observations of Upper Atmosphere Ozone and Chlorine Monoxide

UARS MLS observations of stratospheric ozone and chlorine monoxide are described. Enhanced concentrations of ClO, the predominant form of reactive chlorine responsible for ozone depletion, are seen within both the northern and southern winter polar vortices. In the southern hemisphere, this leads directly to the development of the annual Antarctic ozone hole. While ozone depletion is also observed in the north, it is less severe and there is considerable interannual variability.

stratosphere ozone chlorine monoxide Microwave Lim↗

Experimental and Theoretical Studies of Atmosphereic Inorganic Chlorine Chemistry

Over the last five years substantial progress has been made in defining the realm of new chlorine chemistry in the polar stratosphere. Application of existing experimental techniques to potentially important chlorine-containing compounds has yielded quantitative kinetic and spectroscopic data as well as qualitative mechanistic insights into the relevant reactions.

Atmosphere Chlorine Chemistry↗

Decline in Antarctic Ozone Depletion and Lower Stratospheric Chlorine Determined From Aura Microwave Limb Sounder Observations

Attribution of Antarctic ozone recovery to the Montreal protocol requires evidence that (1)Antarctic chlorine levels are declining and (2) there is a reduction in ozone depletion in response to achlorine decline. We use Aura Microwave Limb Sounder measurements of O3, HCl, and N2O to demonstratethat inorganic chlorine (Cly) from 2013 to 2016 was 223 ± 93 parts per trillion lower in the Antarctic lowerstratosphere than from 2004 to 2007 and that column ozone depletion declined in response. The mean Clydecline rate, ~0.8%/yr, agrees with the expected rate based on chlorofluorocarbon lifetimes. N2Omeasurements are crucial for identifying changes in stratospheric Cly loading independent of dynamicalvariability. From 2005 to 2016, the ozone depletion and Cly time series show matching periods of decline,stability, and increase. The observed sensitivity of O3 depletion to changing Cly agrees with the sensitivitysimulated by the Global Modeling Initiative chemistry transport model integrated

Ozone recovery↗

Chlorine Worth Study Nuclear Data

The Chlorine Worth Study (CWS) was a series of experiments that took place at the National Criticality Experiments Research Center (NCERC), operated by Los Alamos National Laboratory (LANL). The focus of the experiments was to develop new integral benchmarks for the International Criticality Safety Benchmark Evaluation Project (ICSBEP) Handbook with high sensitivity to chlorine in the thermal neutron energy region and which match sensitivities of aqueous chloride operations at LANL. This work discusses the experiment and how the experimental and simulated results using different nuclear data libraries compare to each other.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Chlorine Nuclear Data Evaluation Aided Through New LANSCE Measurements

The collaboration between the Los Alamos National Laboratory Neutron Science Center (LANSCE) and TerraPower LLC enables the enhanced understanding of fast spectrum critical systems consisting of chlorine. Specifically, TerraPower is interested in updating the nuclear data for the stable isotopes of chlorine, 35 Cl and 37 Cl, because these nuclides are the primary constituents of the chloride fuel salt in the Molten Chloride Reactor Experiment (MCRE), for which TerraPower is leading the design. The Cooperative Research and Development Agreement (CRADA) between the parties is funded by DOE’s Office of Nuclear Energy’s Gateway for Accelerated Innovation in Nuclear (GAIN) initiative to provide the nuclear community with access to the technical, regulatory, and financial support necessary to motivate innovative nuclear reactor technologies toward commercialization. New measurements of 35 Cl(n,p total ) and 35 Cl(n,α total ) were completed at LANSCE to constrain the reaction theory models that are used to generate the updated evaluations. The updated evaluations were then tested across the sensitivities of the MCRE by TerraPower to provide direct feedback to the evaluation for application specific sensitivities.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

The reduction of chlorine on carbon in AlCl3-KCl-NaCl melts

Using a rotating vitreous carbon disk electrode, the kinetic parameters for chlorine reduction in an AlCl3-KCl-NaCl (57.5-12.5-30 mol percent) melt were determined. It was found that the reduction of chlorine occurs according to two paths, with the first step probably being rate-determining.

Holleck, G. L.↗

The surface structure of titanium and its interaction with bromine and chlorine

The surface structure and composition of titanium have been studied by electron diffraction and Auger electron spectroscopy in the temperature range 25 to 850 C. Atomically clean, well-defined Ti surfaces were obtained by a combination of argon ion sputtering and thermal treatment at 700 to 800 C. A series of surface superstructures was observed as the crystal temperature was gradually decreased. The development of the superstructures is best explained as due to surface reconstruction as a result of surface relaxation. The interaction of bromine and chlorine vapors with clean Ti surfaces was investigated in the temperature range 25 to 500 C. Bromine exposure at room temperature gave rise to an amorphous surface layer, which on annealing transformed into an epitaxial TiBr2 structure. Chlorine interaction resulted in the formation of an epitaxial TiCl3 on both cold and hot Ti surfaces. Surface impurities inhibited the chemical interaction process on the Ti surface.

Khan, I. H.↗

Photoionization cross sections for atomic chlorine using an open-shell random phase approximation

The use of the Random Phase Approximation with Exchange (RPAE) for calculating partial and total photoionization cross sections and photoelectron angular distributions for open shell atoms is examined for atomic chlorine. Whereas the RPAE corrections in argon (Z=18) are large, it is found that those in chlorine (Z=17) are much smaller due to geometric factors. Hartree-Fock calculations with and without core relaxation are also presented. Sizable deviations from the close coupling results of Conneely are also found.

Starace, A. F.↗