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At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Surface chlorination of IrO2(110) by HCl

The ability to controllably chlorinate metal-oxide surfaces can provide opportunities for designing selective oxidation catalysts. In the present study, we investigated the surface chlorination of IrO2(110) by HCl using temperature programmed reaction spectroscopy (TPRS), x-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. We find that exposing IrO2(110) to HCl, followed by heating to 650 K in ultrahigh vacuum, produces nearly equal quantities of on-top and bridging Cl atoms on the surface, Clt and Clbr, where the Clbr atoms replace O-atoms that are removed from the surface by H2O formation. After HCl adsorption at 85 K, only H2O desorbs at low Cl coverages during TPRS, but HCl begins to desorb in increasing yields as the Cl coverage is increased above about 0.5 monolayer (ML). The desorption of Cl2 was not observed under any conditions, in good agreement with the high barrier for this reaction predicted by DFT. A maximum Cl coverage of 1 ML, with nearly equal coverages of Clt and Clbr atoms, could be generated by reacting HCl with IrO2(110) in UHV. Our results suggest that a kinetic competition between recombinative HCl and H2O desorption under the conditions studied limits the saturation Cl coverage to a value less than the 2 ML maximum predicted by thermodynamics. XPS further shows that the partitioning of Cl between the Clt and Clbr states can be altered by subjecting partially chlorinated IrO2(110) to reductive or oxidative treatments, demonstrating that the Cl site population can change dynamically in response to the gas environment. Our results provide insights for understanding the chlorination of IrO2(110) by HCl and can enable future experimental studies to determine how Cl-modification alters the surface chemical reactivity of IrO2(110) and potentially enhances selectivity toward partial oxidation chemistry.

Chemistry↗
DOE OSTI2013

Process Improvement: Reduce unplanned chlorine delivery shutdowns for the plutonium purification processing [Slides]

Chlorine delivery system used by MET-1 leaked in 2012 and operations were suspended. The existing chlorine gas deliver and detection system is in need of upgrade or replacement. It is reaching the end of the 25 year design life. The current system is a bench scale system that is now running on a continuous basis ~ 10 hours per day. Chlorine is used as a reagent for a number of nuclear material metal preparation and purification applications at LANL Plutonium Facility. MET-1 uses Chlorine for purification. Benefits of improving this process immediately benefit MET-1 who deals with the throughput of Plutonium on the technical and engineering side and benefits NCO-1&2 on the safety side.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Complete Non-Radioactive Operability Tests for Cladding Hull Chlorination

Non-radioactive operability tests were made to test the metal chlorination reactor and condenser and their accessories using batch chlorinations of non-radioactive cladding samples and to identify optimum operating practices and components that need further modifications prior to installation of the equipment into the hot cell for tests on actual used nuclear fuel (UNF) cladding. The operability tests included (1) modifications to provide the desired heating and reactor temperature profile; and (2) three batch chlorination tests using, respectively, 100, 250, and 500 g of cladding. During the batch chlorinations, metal corrosion of the equipment was assessed, pressurization of the gas inlet was examined and the best method for maintaining solid salt product transfer through the condenser was determined. Also, additional accessing equipment for collection of residual ash and positioning of the unit within the hot cell were identified, designed, and are being fabricated.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2020

Application of Gaussian Bayes classifier to differentiate chlorine-based chemical agents

The Portable Isotopic Neutron Spectroscopy (PINS) is a commercialized system developed by Idaho National Laboratory (INL) to examine chemical warfare agents (CWA) non-destructively, utilizing Prompt Gamma Neutron Activation Analysis (PGNAA) techniques. The PINS system takes advantage of a high-resolution gamma-ray spectrum from a mechanically-cooled high-purity germanium (HPGe) detector. One of the difficult technical challenges is to discriminate the chlorine-based chemical agents. Especially, CN, CNB, CNS and CG have similar chemical compositions to make it hard to discriminate them with a higher confidence. Current identification algorithms for PINS systems with 252-Cf sources have been improved and updated continuously as more field data became available, and new algorithms was studied to complement the current algorithms by adopting the Gaussian Bayes classifier. These new algorithms were intended to be applied to a subset of chlorine-based chemical agents, and their main goal is discriminate CN, CNB, CNS and CG with their ratios of the chlorine neutron inelastic 1763keV peak to the chlorine thermal neutron capture 1959keV peak, which is referred to as the “Cl i/c” or “clic” ratio in this study. The Cl i/c ratios were assumed to follow Gaussian distributions with the means and the standard deviations unique to their corresponding chemical agents. The prior probabilities of these four chemical agents were optimized with a collection of field data to achieve the best performance in terms of precision or positive predictive value (PPV). Finally, their posterior probabilities as functions of the Cl i/c ratio were implemented in the current version of PINS analysis software in order to be tested with more field data.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

Quantify Contaminant Partitioning in Advanced Chlorination Process

Chlorination of the zirconium in spent fuel cladding has been identified as a significant means of Zr recovery and purification, enabling a 25% (wt.) or greater reduction in waste requiring geologic disposition. Several chlorinating agents have been identified over the last few years, including gases and liquids. In particular, the interactions of sulfur-chloride solvents with zirconium may allow the separation of zirconium from uranium with the selective formation of ZrCl 4 . This report reviews what is known about reactions between chlorinating agents, uranium metal and oxide, Zircaloy and its alloying elements, and fission plus activation products. Plans for testing the feasibility of applying advanced chlorination methods developed for zirconium recycling to the front end of the recycling of spent nuclear fuel are also included.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Behavior of contaminants and simulant fission products in the advanced chlorination process

The University of Tennessee, Knoxville and Oak Ridge National Laboratory have completed proof-of principle testing on an advanced sulfur-based zirconium and aluminum chlorination process for the recovery of Zr or Al from spent fuel claddings and purification of the products. This process could be used to recover hafnium-free nuclear-grade zirconium for reuse or disposal as low-level waste. Testing showed that even non-optimized reaction protocols could produce zirconium product streams from simulated irradiated fuel with purities >90%. The chlorination process was tested on representative fission product species that would be found in Advanced Test Reactor fuel (ATR). First, fission product generation was determined through modeling and simulation of the ATR. The generation of fission products was used to selected contaminants and potentially volatile fission product simulants for laboratory testing. The goal is to identify which species may react with the sulfur-chlorine reagents and be transported into the advanced chlorination off-gas.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

The Influence of Transitional Metal Dopants on Reducing Chlorine Evolution during the Electrolysis of Raw Seawater

Electrocatalytic water splitting is a possible route to the expanded generation of green hydrogen; however, a long-term challenge is the requirement of fresh water as an electrolyzer feed. The use of seawater as a direct feed for electrolytic hydrogen production would alleviate fresh water needs and potentially open an avenue for locally generated hydrogen from marine hydrokinetic or off-shore power sources. One environmental limitation to seawater electrolysis is the generation of chlorine as a competitive anodic reaction. This work evaluates transition metal (W, Co, Fe, Sn, and Ru) doping of Mn-Mo-based catalysts as a strategy to suppress chlorine evolution while sustaining catalytic efficiency. Electrochemical evaluations in neutral chloride solution and raw seawater showed the promise of a novel Mn-Mo-Ru electrode system for oxygen evolution efficiency and enhanced catalytic activity. Subsequent stability testing in a flowing raw seawater flume highlighted the need for improved catalyst stability for long-term applications of Mn-Mo-Ru catalysts. This work highlights that elements known to be selective toward chlorine evolution in simple oxide form (e.g., RuO2) may display different trends in selectivity when used as isolated dopants, where Ru suppressed chlorine evolution in Mn-based catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1972

Inhibition of the ablation rate of graphite by gaseous chlorine.

Investigation of the inhibiting effect of gaseous chlorine on the ablation rate of graphite. It is shown that small amounts of chlorine gas, when present in a supersonic high-temperature air environment, can inhibit the ablation rate of graphite and depress its surface temperature below that measured in pure air. The ablation inhibition performance of chlorine is presented in graphs in terms of mass loss rate and surface temperature depression as a function of chlorine concentration.

Maahs, H. G.↗
NASA NTRS1981

Chlorine oxide in the stratospheric ozone layer Ground-based detection and measurement

Stratospheric chlorine oxide, a significant intermediate product in the catalytic destruction of ozone by atomic chlorine, has been detected and measured by a ground-based 204 GHz, millimeter-wave receiver. Data taken at latitude 42 deg N on 17 days between January 10 and February 18, 1980 yield an average chlorine oxide column density of approximately 1.05 x 10 to the 14th/sq cm or approximately 2/3 that of the average of eight in situ balloon flight measurements (excluding the anomalously high data of July 14, 1977) made over the past four years at 32 deg N. Less chlorine oxide below 35 km and a larger vertical gradient than predicted by theoretical models of the stratospheric ozone layer are found.

Parrish, A.↗
NASA NTRS1981

Matrix spectroscopic studies of chlorine atom-ozone reaction products

A spectroscopic study is presented of the matrix-isolated products of the direct combination reaction of chlorine atoms with ozone and of the microwave discharge reaction of chlorine and oxygen. Infrared spectra in the wavenumber range 2000 to 200 per cm were recorded for reaction products trapped by the condensation of a matrix of solid argon. Evidence for the formation of the ClO radical as well as the ClOO and ClClO radicals during the direct chlorine-ozone reaction is obtained, however no evidence is found for the presence of asymmetric ClO3 under conditions thought favorable for its formation. The ClO molecule is also observed following the microwave discharge reaction of chlorine and oxygen in argon in the isotopic forms (Cl-35)(O-16), (Cl-37)(O-16), (Cl-35)(O-18), and (Cl-37)(O-18). It is noted that the vibrational frequency for the (Cl-35)(O-16) radical at 849.2 per cm is blue-shifted 5 per cm above its gas-phase fundamental.

Carter, R. O., III↗
NASA NTRS1986

Chlorine chemistry in the Antarctic stratosphere - Impact of OClO and Cl2O2 and implications for observations

Theories have been proposed to relate the reduction of O3 during Antarctic spring to catalytic cycles involving chlorine and bromine species. A necessary condition for any chlorine-catalyzed scheme is that a large fraction of the chlorine must be in the form of ClO in the lower stratosphere. It has been suggested that these high levels of ClO could be maintained by fast heterogeneous reactions, whose rates are not known at present. Model calculations based on the above mechanisms predict considerable amounts of OClO and Cl2O2, particularly during the night. Results of calculations of the diurnal variations of ClO, OClO, and Cl2O2 during Antarctic spring are presented for different cases. Results from the calculations suggest that coincident measurements of the total column abundance and diurnal variation of ClO and OClO may help constrain key aspects of the proposed chemical mechanisms. Removal of O3 by the catalytic cycle involving Cl2O2 could be as important as that involving BrO for present levels of chlorine, provided that Cl2O2 photolyzes rapidly to yield Cl and ClO2. It is shown that there is no synergy between these two cycles, since they both compete for the available ClO.

Rodriguez, Jose M.↗
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 NTRS1990

Natural chlorine and fluorine in the atmosphere, water and precipitation

The geochemical cycles of chlorine and fluorine are surveyed and summarized as framework for the understanding of the global natural abundances of these species in the atmosphere, water, and precipitation. In the cycles the fluxes into and out of the atmosphere can be balanced within the limits of our knowledge of the natural sources and sinks. Sea salt from the ocean surfaces represent the predominant portion of the source of chlorine. It is also an important source of atmospheric fluorine, but volcanoes are likely to be more important fluorine sources. Dry deposition of sea salt returns about 85 percent of the salt released there. Precipitation removes the remainder. Most of the sea salt materials are considered to be cyclic, moving through sea spray over the oceans and either directly back to the oceans or deposited dry and in precipitation on land, whence it runs off into rivers and streams and returns to the oceans. Most of the natural chlorine in the atmosphere is in the form of particulate chloride ion with lesser amounts as gaseous inorganic chloride and methyl chloride vapor. Fluorine is emitted from volcanoes primarily as HF. It is possible that HF may be released directly form the ocean surface but this has not been confirmed by observation. HCl and most likely HF gases are released into the atmosphere by sea salt aerosols. The mechanism for the release is likely to be the provision of protons from the so-called excess sulfate and HNO3. Sea salt aerosol contains fluorine as F(-), MgF(+), CaF(+), and NaF. The concentrations of the various species of chlorine and fluorine that characterize primarily natural, unpolluted atmospheres are summarized in tables and are discussed in relation to their fluxes through the geochemical cycle.

Friend, James P.↗
NASA NTRS1991

Ozone depletion and chlorine loading potentials

The recognition of the roles of chlorine and bromine compounds in ozone depletion has led to the regulation or their source gases. Some source gases are expected to be more damaging to the ozone layer than others, so that scientific guidance regarding their relative impacts is needed for regulatory purposes. Parameters used for this purpose include the steady-state and time-dependent chlorine loading potential (CLP) and the ozone depletion potential (ODP). Chlorine loading potentials depend upon the estimated value and accuracy of atmospheric lifetimes and are subject to significant (approximately 20-50 percent) uncertainties for many gases. Ozone depletion potentials depend on the same factors, as well as the evaluation of the release of reactive chlorine and bromine from each source gas and corresponding ozone destruction within the stratosphere.

Pyle, John A.↗
NASA NTRS1993

A 3D simulation of the early winter distribution of reactive chlorine in the north polar vortex

Early in December 1991, high values of ClO are seen by the Microwave Limb Sounder (MLS) on the Upper Atmosphere Research Satellite at latitudes south of areas of temperatures cold enough to form polar stratospheric clouds (PSCs). A 3D simulation shows that the heterogeneous conversion of chlorine reservoirs to reactive chlorine on the surfaces of PSCs (processing) takes place at high latitudes. Often the processed air must be transported to lower latitudes, where the reactive chlorine is photochemically converted to ClO, to be observed by MLS. In this simulation, one incidence of cold temperatures is associated with an anticyclone, and a second with a cyclone. The transport of processed air associated with the anticyclone is marked by shearing; a decrease in the maximum of the processed air is accompanied by growth of the area influenced by the processing. In contrast, the air processed in the cyclonic event spreads more slowly. This shows that transport and shearing is a crucial element to the evolution of reactive chlorine associated with a processing event. In particular, transport and shearing, as well as photochemical processes, can cause variations in observed ClO.

Douglass, A.↗
NASA NTRS1995

The fate of atmospheric phosgene and the stratospheric chlorine loadings of its parent compounds: CCl4, C2Cl4, C2HCL3, CH3CCl3, and CHCl3

A study of the tropospheric and stratospheric cycles of phosgene is carried out to determine its fate and ultimate role in controlling the ozone depletion potentials of its parent compounds. Tropospheric phosgene is produced from the OH-initiated oxidation of C2Cl4, CH3CCl3, CHCl3, and C2HCl3. Simulations using a two-dimensional model indicate that these processes produce about 90 pptv/yr of tropospheric phosgene with an average concentration of about 18 pptv, in reasonable agreement with observations. We estimate a residence time of about 70 days for tropospheric phosgene, with the vast majority being removed by hydrolysis in cloudwater. Only about 0.4% of the phosgene produced in the troposphere avoids wet removal and is transported to the stratosphere, where its chlorine can be released to participate in the catalytic destruction of ozone. Stratospheric phosgene is produced from the photochemical degradation of CCl4, C2Cl4, CHCl3, and CH3CCl3 and is removed by photolysis and downward transport to the troposphere. Model calculations, in good agreement with observations, indicate that these processes produce a peak stratospheric concentration of about 25-30 pptv at an altitude of about 25 km. In contrast to tropospheric phosgene, stratospheric phosgene is found to have a lifetime against photochemical removal of the order of years. As a result, a significant portion of the phosgene that is produced in the stratosphere is ultimately returned to the troposphere, where it is rapidly removed by clouds. This phenomenon effectively decreases the amount of reactive chlorine injected into the stratosphere and available for ozone depletion from phosgene's parent compounds. A similar phenomenon due to the downward transport of stratospheric COFCl produced from CFC-11 is estimated to cause a 7% decrease in the amount of reactive chlorine injected into the stratosphere from this compound. Our results are potentially sensitive to a variety of parameters, most notably the rate of reaction of phosgene with sulfate aerosols. However, on the basis of the observed vertical distribution of COCl2, we estimate that the reaction of COCl2 with sulfate aerosol most likely has a gamma less than 5 x 10(exp -5) and, as a result, has a negligible impact on the stratospheric chlorine loadings of the phosgene parent compounds.

Kindler, T. P.↗
NASA NTRS1999

A Study of Stratospheric Aerosols and Their Effect on Inorganic Chlorine Partitioning Using Balloon, In Situ, and Satellite Observations

Heterogeneous reactions on the surface of aerosols lead to a decrease in the concentration of nitrogen radicals and an increase in the concentration of chlorine and hydrogen radical species. As a consequence, enhanced sulfate aerosol levels in the lower stratosphere resulting from volcanic eruptions lead to lower concentrations of ozone due to more rapid loss by chlorine and hydrogen radicals. This study focuses on continuing the effort to quantify the effect of sulfate aerosols on the partitioning of inorganic chlorine species at midlatitudes. The study begins with an examination of balloon-borne measurements of key chlorine species obtained by the JPL MkIV interferometer for different aerosol loading conditions. A detailed comparison of the response of HCl to variations in aerosol surface area observed by MkIV, ER-2 instruments, HALOE, and ATMOS is carried out by examining HCl vs CH4 correlation diagrams, since CH4 is the only tracer measured on each platform. Finally, the consistency between theory and observed changes in ClO and HCl due to variations in aerosol surface area is examined.

Osterman, G. B.↗
NASA NTRS1994

Ab Initio Calculations of Singlet and Triplet Excited States of Chlorine Nitrate and Nitric Acid

Ab initio calculations of vertical excitations to singlet and triplet excited states of chlorine nitrate and nitric acid are reported. The nature of the electronic transitions are examined by decomposing the difference density into the sum of detachment and attachment densities. Counterparts for the three lowest singlet excited states of nitric acid survive relatively unperturbed in chlorine nitrate, while other low-lying singlet states of chlorine nitrate appear to be directly dissociative in the ClO chromophore. These results suggest an assignment of the two main peaks in the experimental chlorine nitrate absorption spectrum. In addition, triplet vertical excitations and the lowest optimized triplet geometries of both molecules are studied.

Grana, Ana M.↗