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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
NASA NTRS1996

Airborne Instruments for the In Situ Detection of ClONO2, NO2, ClO, and BrO in the Stratosphere

Design and construction of an in situ sensor for the detection of stratospheric ClONO2, ClO, BrO, and NO2, was conceived as a two-year program. The experiment has two novel components: a resistive silicon thermal dissociation heater used to fragment ClONO2 into ClO and NO2 and a laser-induced fluorescence sensor for N02. These two new components are integrated into an experiment that uses technology developed in our labs for the ER-2 ClO and ER-2 HO(X) instruments. During the first year we reconstructed our laboratory prototypes for ClONO2 and NO2 detection and made substantial improvements in the calibration apparatus. Results from these laboratory experiments have been used to refine the design of the flight instrument. During this year we began the design of all of the long-lead items required to produce a flight instrument: including the design and fabrication of the air flow system used to direct stratospheric air to our halogen sensors, design and prototyping of an aircraft-compatible thermal dissociation heater, and development and test of a new high powered laser system. Finally, we have designed and released for fabrication several subsystems.

Anderson, James G.↗
NASA NTRS1995

Interhemispheric differences in polar stratospheric HNO3, H2O, ClO, and O3

Simultaneous global measurements of nitric acid (HNO3), water (H2O), chlorine monoxide (ClO), and ozone (O3) in the stratosphere have been obtained over complete annual cycles in both hemispheres by the Microwave Limb Sounder on the Upper Atmosphere Research Satellite. A sizeable decrease in gas-phase HNO3 was evident in the lower stratospheric vortex over Antarctica by early June 1992, followed by a significant reduction in gas-phase H2O after mid-July. By mid-August, near the time of peak ClO, abundances of gas-phase HNO3 and H2O were extremely low. The concentrations of HNO3 and H2O over Antarctica remained depressed into November, well after temperatures in the lower stratosphere had risen above the evaporation threshold for polar stratospheric clouds, implying that denitrification and dehydration had occurred. No large decreases in either gas-phase HNO3 or H2O were observed in the 1992-1993 Arctic winter vortex. Although ClO was enhanced over the Arctic as it was over the Antarctic, Arctic O3 depletion was substantially smaller than that over Antarctica. A major factor currently limiting the formation of an Arctic ozone 'hole' is the lack of denitrification in the northern polar vortex, but future cooling of the lower stratosphere could lead to more intense denitrification and consequently larger losses of Arctic ozone.

Santee, M. L.↗
NASA NTRS1996

The 1988 Arctic Survey, Diurnal Study (Sunrise and Sunset) and Peak Altitude (22 km) Flights for the In Situ Detection of ClO and BrO from the NASA ER-2 Aircraft

Two critical areas of research were addressed successfully by this research. The first involves NASA ER-2 airborne observations of ClO and BrO radical destruction of ozone within the arctic vortex. The second involves the analysis of diurnal variations in ClO, to test the production and loss rates of ClO that constitutes the test for coupling reactions between the chlorine and nitrogen systems. We discuss results from this research in order.

Anderson, James G.↗
NASA NTRS2000

Measurement of ClO and CO2 for ACCENT

Observations have shown that ozone in largely removed in rocket plumes within an hour of launch [M.N. Ross, et al., Nature 390, 62-64, 1997]. Large abundances of chlorine oxide (ClO) were first detected in the fresh plume of a Delta rocket in May of 1998 from the NASA WB-57 during the Air Force RISO campaign by the CORE instrument developed at UC Irvine. Similar abundances were detected a month later in the plume of an ATLAS II rocket. Although the maximum ClO observed in these plumes was twenty-five times larger than the highest values ever observed in the perturbed polar vortices, in a new study, [M.N. Ross, et al., Geophys. Res. Lett., 2000, in press] could not account for observed ozone losses based on known chlorine photochemistry. New measurements were obtained in plumes of Delta, Atlas, and Athena rockets in 1999 during ACCENT with the CORE instrument augmented with a modified LiCor non-dispersed infrared detector for fast-response measurements of carbon-dioxide (CO2). The absolute abundance of this specie constrains the rocket emission stoichiometry, and its relative abundance serves as a tracer of dilution. The combination of ClO and CO2 will provide important new insights into the temporal and spatial evolution of reactive chlorine partitioning and its dependence on rocket motor type.

Toohey, Darin↗
NASA NTRS1999

The Coupling of ClONO2, ClO, and NO2 in the Lower Stratosphere From in Situ Observations Using the NASA ER-2 Aircraft

The first in situ measurements of ClONO2 in the lower stratosphere, acquired using the NASA ER-2 aircraft during the Polar Ozone Loss in the Arctic Region in Summer (POLARIS) mission, are combined with simultaneous measurements of ClO, NO2, temperature, pressure, and the calculated photolysis rate coefficient (J(sub ClONO2)) to examine the balance between production and loss of ClONO2. The observations demonstrate the ClONO2 photochemical steady state measurement, [ClONO2](sup PSS) = k[ClO][No2]/J(sub ClONO2), is in good agreement with the direct measurement, [ClONO2](sup MEAS). For the bulk of the data (80%), where T > 220 K and latitudes > 45 N, [ClONO2](sup PPS) = 1.15 +/- 0.36(1-sigma)[ClONO2](sup MEAS), while for T< 220 K and latitudes < 45 N, the result is somewhat less at 1.01 +/- 0.30. The cause of the temperature and/or latitude trend is unidentified. These results are independent of solar zenith angle and air density, thus there is no evidence in support of a pressure-dependent quantum yield for photodissociation of ClONO2 at wavelengths > 300 nm. These measurements confirm the mechanism by which active nitrogen (NOx = NO + NO2) controls the abundance of active chlorine (Clx = ClO + Cl) in the stratosphere.

Stimpfle, R. E.↗
DOE OSTI2020

Materials Data on Ca(ClO)2 by Materials Project

Ca(ClO)2 crystallizes in the orthorhombic Ccce space group. The structure is one-dimensional and consists of four Ca(ClO)2 ribbons oriented in the (1, 0, 0) direction. Ca is bonded in a 4-coordinate geometry to four equivalent O atoms. There are two shorter (2.34 Å) and two longer (2.38 Å) Ca–O bond lengths. O is bonded in a 3-coordinate geometry to two equivalent Ca and one Cl atom. The O–Cl bond length is 1.71 Å. Cl is bonded in a single-bond geometry to one O atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Correlating Mechanical Sensitivity with Spin Transition in the Explosive Spin Crossover Complex [Fe(Htrz) 3 ] n [ClO 4 ] 2 n

Spin crossover complexes are known to undergo bond length, volume, and enthalpy changes during spin transition. In an explosive spin crossover complex, these changes could affect the mechanical and initiation sensitivity of the explosive and lead to the development of a new class of sensitivity switchable materials. To explore this relationship, the well-known spin crossover compound [Fe(Htrz) 3 ] n [ClO 4 ] 2n (1) was re-evaluated for its explosive properties, and its mechanical impact sensitivity was correlated to spin transition. A variable temperature impact test was developed and used to evaluate the impact sensitivity of 1 in the low spin (LS, S = 0), thermally accessed high spin (HS, S = 2), and mixed LS and HS states. For comparison, the structurally similar Ni compound, [Ni(Htrz) 3 ] n [ClO 4 ] 2n (2), which does not undergo a spin transition at accessible temperatures, was synthesized and characterized, and its explosive properties and variable temperature impact sensitivity measured. These results reveal a correlation between impact sensitivity and spin transition, where 1 exhibits lower impact sensitivity in the LS state and increases in sensitivity upon transition to the HS state. Here, density functional theory was used to predict structural changes that occur upon spin transition that correlate to the change in sensitivity. This demonstrates, for the first time, an explosive spin crossover compound (ExSCO) that exhibits switchable impact sensitivity with a fully reversible internal switching mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Crystal field splittings and magnetic ground state of the square-lattice antiferromagnets YbBi 2 ⁢ClO 4 and YbBi 2 ⁢IO 4 with J eff = $\frac{1}{2}$

Here, we report on the crystal field level splitting and magnetic ground state of the J eff = $\frac{1}{2}$ square lattice antiferromagnets YbBi 2 ⁢ClO 4 and YbBi 2 ⁢IO 4 using powder inelastic neutron scattering (INS) and neutron diffraction measurements. Both compounds exhibit a well-isolated Γ 7 doublet ground state under a tetragonal crystal field environment, confirming a robust J eff = $\frac{1}{2}$ picture with slight XY-type anisotropic character in the g-tensor. Notably, the ground state wave functions closely resemble the Γ 7 doublet expected in the perfect cubic limit, consistent with the nearly cubic ligand configuration of eight O 2- ions surrounding Yb 3+ . Below T N = 0.21 K, YbBi 2 ⁢IO 4 exhibits a stripe long-range magnetic order characterized by an ordering wave vector q m = (1/2, 0, 0) or its symmetry-equivalent (0, 1/2, 0), with magnetic moments aligned along q m . The ordered moment is approximately 79% of the classical prediction, significantly larger than expected from the isotropic J 1 -J 2 model, suggesting the possible involvement of exchange anisotropy in explaining this observation. We show that symmetry-allowed XXZ and bond-dependent anisotropic exchange terms in a square lattice can play a critical role in stabilizing the stripe order and suppressing the moment reduction as observed. These findings establish YbBi 2 ⁢ClO 4 and YbBi 2 ⁢IO 4 as unique platforms for exploring rich J eff = $\frac{1}{2}$ magnetism from two less investigated perspectives: (i) on a square lattice and (ii) within a (nearly) cubic ligand environment.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS1977

Rate constant for formation of chlorine nitrate by the reaction ClO + NO2 + M

The pseudo-first-order decay of ClO in a large excess of NO2 was monitored in a discharge flow/mass-spectrometer apparatus in order to measure the rate constant of the reaction ClO + NO2 + M yields ClONO2 + M for M = He, Ar, and N2 over the temperature range from 248 to 417 K. Numerical results are given for He at 248, 299, 360, and 417 K (1 to 9 torr); for Ar at 298 K (1 to 4 torr); and for N2 at 299, 360, and 417 K (1 to 6 torr). Systematic errors are estimated, and identification of the reaction product is discussed. The results obtained are shown to be in excellent agreement with other recent measurements of the same rate constant.

Leu, M. T.↗
NASA NTRS1977

Reaction rates for O3 + HCl yielding O + O2 + HCl, Cl + O3 yielding ClO + O2, and HCl + O yielding OH + Cl at elevated temperatures

Ozone and a much greater quantity of hydrogen chloride, slightly diluted by oxygen and argon, were heated by a shock wave process to temperatures in the range 480-1300 K at pressures from four to eight atmospheres. From variations in ozone concentration, determined by the attentuation of 2537-A radiation, the rate coefficient for the reaction O3 + HCl yielding O + O2 + HCl was determined to be k1 = (4.0 plus or minus 1.5) x 10 to the minus 10 exp(-10,408/T)cm3/s for temperatures of 480-720 K. From the concentration of ClO remaining at the end of ozone decomposition the rate coefficients for the reactions Cl + O3 yielding ClO + O2 and HCl + O yielding OH + Cl were also deduced for a temperature of about 1100 K.

Park, C.↗
NASA NTRS1977

High resolution absorption cross sections for the A2Pi-X2Pi system of ClO

High-resolution ultraviolet absorption cross-sections for the ClO molecule are obtained, with the aim of facilitating studies of ozone depletion resulting from the injection of chlorofluorocarbons into the atmosphere. The spectroscopic analysis, which involves a frequency-doubled tunable dye laser with a bandwidth of 0.015 A, is described. Studies of the rotational lines of the ClO A 2Pi 3/2-X2Pi 3/2 9-10 band were conducted. Peak cross-sections for the P and R lines of the 9-0 band are found to be 10.0, 9.6, 8.6, 10.6, 10.3, and 9.2 times ten to the negative seventeenth power cm squared, with estimated accuracy of plus or minus 25%. Problems in distinguishing between Cl-35 and Cl-37 absorption are also considered.

Wine, P. H.↗
NASA NTRS1978

Calculated rate constants for the reaction ClO + O yields Cl + O2 between 220 and 1000 deg K

Classical trajectory calculations are presented for the reaction ClO + O yields Cl + O2, a reaction which is an important step in the chlorine-catalyzed destruction of ozone which is thought to occur in the 220 and 1000 K. The calculated rate constant is 4.36 x 10 to the minus 11th power exp (-191/T)cu cm molecule (-1)s(-1) and its value at 300 K is 2.3 plus or minus 10 to the 11th power cu cm molecule (-1)s(-1), about a factor of 2 lower than recent experimental data. The empirical potential energy surface used in the calculations was constructed to fit experimental data for ClO, O2 and ClOO molecules. Other important features of this potential surface, such as the barrier to reaction, were varied systematically and calculations were performed for a range of conditions to determine the best theoretical rate constants. Results demonstrate the utility of classical trajectory methods for determining activation energies and other kinetic data for important atmospheric reactions.

Jaffee, R. L.↗
NASA NTRS1977

Theoretical intensity parameters for the vibration-rotation bands of ClO

Intensity parameters for the vibration-rotation bands of ClO were calculated by evaluating matrix elements of the vibrational eigenfunctions using the theoretical dipole moment curve. These vibrational eigenfunctions are based on realistic Klein-Dunham potentials deduced from experimental values (Coxon et al, 1976) for certain vibrational energy levels. The data can be applied to the interpretation of remote or in situ experiments to deduce stratospheric ClO concentrations from vibration-rotation absorption spectra.

Langhoff, S. R.↗
NASA NTRS1979

Rate constants for the reactions of OH with ClO, Cl2, and Cl2O at 298K

Recent concern about the depletion of stratospheric ozone by chlorine species from the decomposition of chlorofluoromethanes has emphasized the need for laboratory studies of the first reaction steps involved, especially those which control the concentration of the OH and ClO radicals in the stratosphere. Rate constants for the reactions of OH with ClO, Cl2, and Cl2O at 298 K have been determined in a discharge flow system using resonance fluoresence detection. The results are (9.1 + or - 1.3) x 10 to the -12th, (5.5 + or - 0.3) x 10 to the -14th, and (6.5 + or - 0.5) x 10 to the -12th (all in units of cu cm/sec), respectively.

Leu, M. T.↗
NASA NTRS1979

An explanation of the preferential formation of less stable isomers in three-body reactions - Cl + NO2 + M; ClO + NO2 + M

A realistic assessment of the potential depletion of stratospheric ozone due to manmade emissions requires a knowledge of the sources and sinks of the potential threat. The reactions ClO + NO2 + M yield products and Cl + NO2 + M yield products are of interest because they represent possible sink mechanism for both odd chlorine and odd nitrogen species. In this paper, the Troe method (1977) is used to calculate the low-pressure limit rate constants of the above three-body reactions. The result for the Cl + NO2 + M reaction is found to be in excellent agreement with the experimental finding of Niki et al. (1978), where both nitryl chloride and chlorine nitrate are products of the cited reaction. An explanation is proposed to account for apparent discrepancy between the measured rate constants for ClO + NO2 + M in the forward and reverse directions. Stratospheric implications are also discussed.

Chang, J. S.↗
NASA NTRS1980

Product distribution for the reaction of HO2 with ClO

The paper reports the direct measurement of the reaction product HOCl from the reaction of H2O with ClO, and sets an upper limit for the possible product O3, using a discharge flow/mass spectrometry/resonance fluorescence apparatus. The upper limits of the reaction channel producing HCl + O3 are 1.5% at 298 K and 3.0% at 248 K. It is seen that the HCl production rate from the HO2 + ClO reaction could be as large as that from the Cl + CH4 reaction in the lower and middle stratosphere. Thus, this reaction may possibly increase the HCl production rate appreciably and thereby reduce the calculated O3 destruction by chlorofluoromethanes.

Leu, M.-T.↗
NASA NTRS1985

Stratospheric ClO - In-situ detection with a new approach

Stratospheric chlorine monoxide concentrations were measured in situ using a new and improved observational method in which the detection package is lowered on a tether from a balloon-borne platform floating near 40 km altitude and then reeled back up. Two reel down and reel up sequences covering 38 to 31 km produced (ClO) profiles which agree with each other to + or - 12 percent. The measured (ClO) profile falls within the envelope of nine previous fast parachute drop results, but exhibits a different shape, peaking near 32 km as opposed to approximately 39 km for the average of the previous profiles. These results are lower than but consistent with the profiles derived from remote sensing methods, and indicate the need for simultaneous measurements of relevant species.

Brune, Wm. H.↗
NASA NTRS1986

In situ observations of midlatitude stratospheric ClO and BrO

A balloon-borne experiment to measure midlatitude stratospheric BrO and ClO concentrations by NO chemical conversion/atomic resonance fluorescence was flown from Palestine, Texas, on May 20 1986. In this first study of BrO, no signal attributable to BrO was detected, and upper limits (2 sigma uncertainty) between 35 and 24 km altitude give BrO mixing ratios less than 15 pptv. Current models predict mixing ratios that are 1.7 times larger. Measurements of ClO were obtained at less than 0.2-km altitude resolution from 41 to 22 km. The smoothly varying altitude profile lies within the range of two-dimensional model calculations.

Brune, William H.↗