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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 73 records · Page 4
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NASA NTRS1989

Reaction of nonaqueous halogen solutions with YBa2Cu3O(7-x)

The reaction of the surfaces of the new high-temperature superconductor YBa2Cu3O(7-x) with nonaqueous halogen solutions is investigated, and the species formed in the reactions are identified. Treatment of films with HF/EtOH (EtOH = HI in absolute ethanol) results in the formation of an oxyfluoride with Y:Ba:Cu relative concentrations of 1:4:3. Results of X-ray photoelectron spectroscopy of HF-treated films are consistent with the formation of CuF, a compound which does not exist in bulk form. Treatment of films with HCl/EtOH results primarily in the formation of BaCl2, with smaller amounts of YCl3, CuCl, and CuCl2. Treatment with Br2/EtOH or HBr/EtOH results in the formation of YBr3, BaBr2, and CuBr with relative concentrations of 1:4:3.

Vasquez, R. P.↗
NASA NTRS1990

Physical properties of alternatives to the fully halogenated chlorofluorocarbons

Presented here are recommended values and correlations of selected physical properties of several alternatives to the fully halogenated chlorocarbons. The quality of the data used in this compilation varies widely, ranging from well-documented, high accuracy measurements from published sources to completely undocumented values listed on anonymous data sheets. That some of the properties for some fluids are available only from the latter type of source is clearly not the desired state of affairs. While some would reject all such data, the compilation given here is presented in the spirit of laying out the present state of knowledge and making available a set of data in a timely manner, even though its quality is sometimes uncertain. The correlations presented here are certain to change quickly as additional information becomes available.

Mclinden, Mark O.↗
NASA NTRS1990

Relative effects on stratospheric ozone of halogenated methanes and ethanes of social and industrial interest

Four atmospheric modeling groups have calculated relative effects of several halocarbons (chlorofluorocarbons (CFC's)-11, 12, 113, 114, and 115; hydrochlorofluorocarbons (HCFC's) 22, 123, 124, 141b, and 142b; hydrofluorocarbons (HFC's) 125, 134a, 143a, and 152a, carbon tetrachloride; and methyl chloroform) on stratospheric ozone. Effects on stratospheric ozone were calculated for each compound and normalized relative to the effect of CFC-11. These models include the representations for homogeneous physical and chemical processes in the middle atmosphere but do no account for either heterogeneous chemistry or polar dynamics which are important in the spring time loss of ozone over Antarctica. Relative calculated effects using a range of models compare reasonably well. Within the limits of the uncertainties of these model results, compounds now under consideration as functional replacements for fully halogenated compounds have modeled stratospheric ozone reductions of 10 percent or less of that of CFC-11. Sensitivity analyses examined the sensitivity of relative calculated effects to levels of other trace gases, assumed transport in the models, and latitudinal and seasonal local dependencies. Relative effects on polar ozone are discussed in the context of evolving information on the special processes affecting ozone, especially during polar winter-springtime. Lastly, the time dependency of relative effects were calculated.

Fisher, Donald A.↗
NASA NTRS1993

The Halogen Occultation Experiment

The Halogen Occultation Experiment (HALOE) uses solar occultation to measure vertical profiles of O3, HCl, HF, CH4, H2O, NO, NO2, aerosol extinction, and temperature versus pressure with an instantaneous vertical field of view of 1.6 km at the earth limb. Latitudinal coverage is from 80 deg S to 80 deg N over the course of 1 year and includes extensive observations of the Antarctic region during spring. The altitude range of the measurements extends from about 15 km to about 60-130 km, depending on channel. Experiment operations have been essentially flawless, and all performance criteria either meet or exceed specifications. Internal data consistency checks, comparisons with correlative measurements, and qualitative comparisons with 1985 atmospheric trace molecule spectroscopy (ATMOS) results are in good agreement. Examples of pressure versus latitude cross sections and a global orthographic projection for the September 21 to October 15, 1992, period show the utility of CH4, HF, and H2O as tracers, the occurrence of dehydration in the Antarctic lower stratosphere, the presence of the water vapor hygropause in the tropics, evidence of Antarctic air in the tropics, the influence of Hadley tropical upwelling, and the first global distribution of HCl, HF, and NO throughout the stratosphere. Nitric oxide measurements extend through the lower thermosphere.

Russell, James M., III↗
NASA NTRS1994

Long term trend of selected halogenated hydrocarbons

The so-called 'Library of Background Air' at the Oregon Graduate Institute was used to determine the trend in volume mixing ratios of selected halogenated hydrocarbons in the time period 1977-1989. This library consists of background air samples most of them taken at Cape Meares (Oregon). For storage stainless steel containers are used. Tests have shown the gases under consideration to be stable in these containers. Analyses using a GC/MS-system were performed for the CFCs 11, 12, 12B1 (HALON 1211, CBrClF2), 22, 113, 114 and CH3Cl, CH3Br, CH3CCl3, CCl4. The advantage of this unique investigation: different aged air samples are analyzed at the same time with the same instrument. No calibrations or intercalibrations are needed. All data are presented in normalized mixing ratios versus time. We discuss the results, derive rate constants and present a formula to describe the nonlinear increases.

Borchers, R.↗
NASA NTRS1994

An overview of the Halogen Occultation Experiment (HALOE) and preliminary results

The Halogen Occultation Experiment (HALOE) experiment has observed vertical profiles and pressure versus latitude cross sections of temperature HCl, HF, CH4, H2O, NO, NO2, O3, and aerosols over the range from 80 deg S to 80 deg N. An in-orbit precision of better than 0.3 ppbv has been demonstrated for HCl, HF, NO, NO2 and less than 0.6 ppmv for the other channels. Comparisons with correlative measurements at this early stage are encouraging. Nitric oxide has been observed over the range from the upper troposphere to 130-km. Latitudinal cross sections of the long-lived tracers CH4 and HF show clear indications of the effect of the general circulation.

Russell, J. M., III↗
NASA NTRS1995

Aerosol effects and corrections in the Halogen Occultation Experiment

The eruptions of Mt. Pinatubo in June 1991 increased stratospheric aerosol loading by a factor of 30, affecting chemistry, radiative transfer, and remote measurements of the stratosphere. The Halogen Occultation Experiment (HALOE) instrument on board Upper Atmosphere Research Satellite (UARS) makes measurements globally for inferring profiles of NO2, H2O, O3, HF, HCl, CH4, NO, and temperature in addition to aerosol extinction at five wavelengths. Understanding and removing the aerosol extinction is essential for obtaining accurate retrievals from the radiometer channels of NO2, H2O and O3 in the lower stratosphere since these measurements are severely affected by contaminant aerosol absorption. If ignored, aerosol absorption in the radiometer measurements is interpreted as additional absorption by the target gas, resulting in anomalously large mixing ratios. To correct the radiometer measurements for aerosol effects, a retrieved aerosol extinction profile is extrapolated to the radiometer wavelengths and then included as continuum attenuation. The sensitivity of the extrapolation to size distribution and composition is small for certain wavelength combinations, reducing the correction uncertainty. The aerosol corrections extend the usable range of profiles retrieved from the radiometer channels to the tropopause with results that agree well with correlative measurements. In situations of heavy aerosol loading, errors due to aerosol in the retrieved mixing ratios are reduced to values of about 15, 25, and 60% in H2O, O3, and NO2, respectively, levels that are much less than the correction magnitude.

Hervig, Mark E.↗
NASA NTRS1994

Observations of stratospheric hydrogen fluoride by halogen occultation experiment (HALOE)

The Halogen Occultation Experiment (HALOE) Hydrogen Fluoride (HF) channel on the Upper Atmospheric Research Satellite (UARS) is providing the first global measurements of stratospheric HF, the dominant flourine reservoir in the atmosphere. This paper describes the latitudinal and seasonal variations of HALOE-observed HF in terms of vertical profiles, altitude/latitude cross sections, and column abundances. The HF global distribution shows a 'tracerlike' structure and its column amount increases with latitude, in agreement with previous aircraft measurements of the HF column amount. A comparison between the HALOE HF column above 20 km and the ATMOS 1985 measurements is used to estimate the annual rate of increase of stratospheric HF. Exponential rates of 4.9-6.6%/yr and linear growth rates of 6-8.6%/yr in 1985 and 4.3-5.5%/yr in 1992-1993 are found. HALOE HF measurements during the 1993 Antarctic spring are briefly described. This species behaves like a conserved tracer and its distribution shows an area of enhanced mixing ratios correlated with the polar vortex that has a clear latitude boundary. Finally, simulated HF distributions by the National Center for Atmospheric Research (NCAR) two-dimensional model are used to compare with HALOE observations of HF. Reasonable agreements in the global structure and the absolute amount of HF are found. The differences between the model and the observed results indicate the need for improving treatment of atmospheric dynamics and fluorine-related chemical parameters in the model simulations.

Luo, M.↗
NASA NTRS1995

An analysis of the Antarctic Halogen Occultation Experiment trace gas observations

Analysis of the version 16 Halogen Occultation Experiment (HALOE) CH4 data shows that this long-lived trace gas is well correlated with potential vorticity (PV) computed from National Meteorological Center balanced winds. Analyzing late September and October 1992 data, we show that very low CH4 values are confined to the interior of a vortex edge defined by the maximum gradient in PV. The CH4 and HF time tendency is used to estimate the descent rate in the Antarctic vortex. After removing a component of the trend correlated with the HALOE sampling pattern, we compute the lower stratosphere vertical descent rates and net heaing rates in the spring Antarctic vortex. Our computations of the spring Antarctic vortex heating rates give -0.5 to -0.1 K/day. Over the winter season, the overall lower stratospheric descent rate averages about 1.8-1.5 km/month. These computations are in line with radiative transfer estimates of the heating and descent rate. The HALOE data thus appear to be consistent with the picture of an isolated lower stratospheric Antarctic vortex.

Schoeberl, Mark R.↗
NASA NTRS1995

Rate constants and temperature dependences for the reactions of hydroxyl radical with several halogenated methanes, ethanes, and propanes by relative rate measurements

Rate constants of 15 OH reactions with halogen-substituted alkanes, C1 to C3, were studied using a relative rate technique in the temperature range 283-403 K. Compounds studied were CHF2Cl (22), CHF2Br (22B), CH3F (41), CH2F2 (32), CHF3 (23), CHClFCCl2F (122a), CHCl2CF3 (123), CHClFCF3 (124), CH3CF3 (143a), CH3CH2F (161), CF3CHFCF3 (227ea), CF3CH2CF3 (236fa), CF3CHFCHF2 (236ea), and CHF2CF2CH2F (245ca). Using CH4, CH3CCl3, CF3CF2H, and C2H6 as primary reference standards (JPL 92-20 rate constants), absolute rate constants are derived. Results are in good agreement with previous experimental results for six of the compounds studied, including CHF2Cl, CHF2Br, CH2F2, CH3CF3, CHFClCFCl2, and CF3CHFCF3. For the remainder the relative rate constants are lower than those derived from experiments in which OH loss was used to measure the reaction rate. Comparisons of the derived Arrhenius A factors with previous literature transition-state calculations show order of magnitude agreement in most cases. However, the experimental A factors show a much closer proportionality to the number of H atoms in the molecule than is evident from the transition state calculations. For most of the compounds studied, an A factor of (8 +/- 3)E-13 cm(exp 3)/(molecule s) per C-H bond is observed. A new measurement of the ratio k(CH3CCl3)/k(CH4) is reported that is in good agreement with previous data.

Hsu, K.-J.↗
NASA NTRS1996

Scientific Studies in Association with the Halogen Occultation Experiment

This work examines measurements of ozone, NO, NO2, and HCl made by the Halogen Occultation Experiment (HALOE) to track chemical change in the stratosphere. In addition, HALOE observations of two long-lived species, HF and CH4, are used as tracers to distinguish between change due to transport processes and change due to chemistry. The first study investigates the response of NO(x), (NO and NO2) and ozone to the presence of large amounts of sulfate aerosol in the stratosphere following the 1991 eruption of Mount Pinatubo. As the Pinatubo aerosol cleared the atmosphere at 17 mb (about 27-28 km), the partitioning of total reactive nitrogen shifted more toward NO(x), and ozone amounts declined. This trend is opposite that observed at lower altitudes. The second study examines the chemical aftermath of severe ozone depletion over Antarctica in spring. When ozone levels drop to a threshold amount (about 1 ppm near 20 km), the partitioning of the total chlorine family shifts rapidly from reactive species to the reservoir molecule HCl. This sudden repartitioning shuts down further ozone loss and may be significant as filaments of air peel off the polar vortex and mix with mid-latitude air.

Mickley, Lorretta J.↗
NASA NTRS1997

Laboratory Investigations of Stratospheric Halogen Chemistry

A final report for the NASA-supported project on laboratory investigations of stratospheric halogen chemistry is presented. In recent years, this project has focused on three areas of research: (1) kinetic, mechanistic, and thermochemical studies of reactions which produce weakly bound chemical species of atmospheric interest; (2) development of flash photolysis schemes for studying radical-radical reactions of stratospheric interest; and (3) photochemistry studies of interest for understanding stratospheric chemistry. The first section of this paper contains a discussion of work which has not yet been published. All subsequent chapters contain reprints of published papers that acknowledge support from this grant.

Wine, Paul H.↗
NASA NTRS1960

Halogen Containing Gases as Lubricants for Crystallized Glass Ceramic Metal Combinations at Temperatures to 1500 F

Pyroceram 9608 (a crystallized glass ceramic) has been considered for use in high-temperature bearing and seal applications. One of the problems encountered with Pyroceram is the lack of availability of lubricants for the temperature range in which this material becomes practical. Experiments were conducted with Pyroceram sliding on various nickel- and cobalt-base alloys using reactive halogen-containing gases as lubricants. Friction and wear data were obtained as a function of sliding velocity and temperature. Studies were made with a hemispherical rider (3/16-in. rad., Pyroceram 9608) sliding in a circumferential path on the flat surface of a rotating disk (2(1/2) in. diam., nickel- or cobalt-base alloys). The specimens were run in an atmosphere of the various gases with a load of 1200 grams, a sliding velocity of 3200 feet per minute, and temperatures from 75 to 1500 F. The gas CF2Br-CF2Br was found to be an effective lubricant for Pyroceram 9608 sliding on Hastelloy R-235 and Inconel X up to 1400 F. The gas CF2Cl-CF2Cl provided effective lubrication for Pyroceram sliding on various cobalt-base alloys at 1000 F.

Buckley, Donald H.↗
NASA NTRS1999

An Evaluation of the Quality of Halogen Occultation Experiment Ozone Profiles in the Lower Stratosphere

The archived ozone profiles from the Halogen Occultation Experiment (HALOE) have already been corrected for the effects of the spectrally varying, interfering absorption due to aerosols composed of aqueous sulfuric acid, and agreement with correlative measurements in the stratosphere is generally excellent. However, comparisons of sets of coincident HALOE and ozonesonde profiles indicate occasional large differences at the lowest levels of the stratosphere. Most of those instances occur at altitudes just below a well-defined minimum in the 5.26 microns channel aerosol extinction profile, whose wavelength dependence is not represented by a sulfuric acid aerosol model. Further, when the aerosol extinction exceeds about 10(exp 3)/ km, the aerosol correction to the ozone channel transmittances is both large and uncertain. After screening out the HALOE ozone profile segments whose corresponding aerosol/cirrus corrections are likely uncertain and after averaging lie ozonesonde profiles into 2.5 km thick layers, we find that the HALOE ozone areas, on average, to within 10% of their coincident ozonesonde measurements down to 100 hPa at tropical/subtropical latitudes and to 200 hPa at extratropical latitudes. A tightening of the coincidence criteria for the comparisons does not improve the mean differences for the sets nearly as much. Part of the variance of the paired differences was also accounted for when the ozonesonde profile values were integrated into those 2.5 km layers, prior to taking differences. This improvement is due mainly to the vertical averaging of the local, higher-resolution ozonesonde data, matching the lower resolution for HALOE ozone in the lower stratosphere. It is concluded that HALOE is providing accurate ozone profiles throughout the lower stratosphere, when its correction for interfering aerosols has been well characterized and when cirrus layers are not indicated.

Bhatt, Praful P.↗
NASA NTRS2001

Establishing the Dependence of [HO2]/[OH] on Temperature, Halogen Loading, O3, and NO(x) Based on in Situ Measurements from the NASA ER-2

In situ observations of OH and HO2 from the Airborne Southern Hemisphere Ozone Experiment/Measurements for Assessing the Effects of Stratospheric Aircraft (ASHOE/MAESA), Stratospheric TRacers of Atmospheric Transport (STRAT), and Polar Ozone Loss in the Arctic Region in Summer (POLARIS) NASA ER-2 field campaigns are used to examine the partitioning of HO(x) in the lower stratosphere (tropopause to approx.21 km) and upper troposphere (approx.10 km to tropopause). These measurements span a latitude range from 70degS to 90degN and a variety of atmospheric conditions as a result of seasonal changes and altitude. The response of the observed [HO2]/[OH] to changes in temperature, [03], [CO], [NO], [CIO], and [BrO] is investigated. The measured ratio is accurately described (approx.+/-10%) by a steady-state model constrained by the measured mixing ratios of O3, CO, NO, CIO, and BrO, where the model is valid for conditions of HO(x) cycling much faster than HO(x) production and loss. The concentration of HO2 depends on [OH], which, to first order, has been observed to be a simple function of the solar zenith angle in the lower stratosphere. The partitioning between OH and HO2 is controlled by the local chemistry between the HO, radicals and O3, CO, NO, CIO, and BrO. The response of [HO(x)] to changes in [NO(x)] and [O3] is demonstrated. Further observations are necessary to illustrate the response of HO(x) to changes in halogen concentrations. A quantitative understanding of [HO2]/[OH] is important, since many of the reactions that control this ratio are directly involved in catalytic removal of O3 in the lower stratosphere and production of O3 in the upper troposphere.

Lanzendorf, E. J.↗
NASA NTRS1995

Ab Initio Studies of Halogen and Nitrogen Oxide Species of Interest in Stratospheric Chemistry

The ability of modern state-of-the art ab initio quantum chemical techniques to characterize reliably the gas-phase molecular structure, vibrational spectrum, electronic spectrum, and thermal stability of fluorine, chlorine, bromine and nitrogen oxide species will be demonstrated by presentation of some example studies. The ab initio results are shown to be in excellent agreement with the available experimental data, and where the experimental data are either not known or are inconclusive, the theoretical results are shown to fill in the gaps and to resolve experimental controversies. In addition, ab initio studies in which the electronic spectra and the characterization of excited electronic states of halogen oxide species will also be presented. Again where available, the ab initio results are compared to experimental observations, and are used to aid in the interpretation of experimental studies.

Lee, Timothy J.↗
NASA NTRS2004

Solubility of HOBr in Acidic Solution and Implications for Liberation of Halogens Via Aerosol Processing

Halogen species are known to catalytically destroy ozone in several regions of the atmosphere. In addition to direct catalytic losses, bromine compounds can indirectly enhance ozone loss through coupling to other radical families. Hypobromous acid (HOBr) is a key species in the linkage of BrOx to ClOx and HOx. The aqueous- phase coupling reaction HOBr + HCI (right arrow) BrCl + H2O may provide a pathway for chlorine activation on sulfate aerosols at temperatures warmer than those required for polar stratospheric cloud formation. We have measured t h e solubility of HOBr in 45 - 70 wt% sulfuric acid solutions. Over the temperature range 201 - 252 K, HOBr is quite soluble in sulfuric acid, H* = 10(exp 4) - 10(exp 7) mol dm(exp -3) atm(exp -1). The expected inverse dependence of H* on temperature was observed, but only a weak dependence on acidity was found. The solubility of HOBr is comparable to that of HBr, indicating that equilibrium concentrations of HOBr could equal or exceed those of HBr in upper tropospheric and lower stratospheric aerosols. Despite the high solubility of HOBr, aerosol volumes are not large enough to sequester a significant fraction of inorganic bromine from the gas phase. Our measurements of HOBr uptake in aqueous sulfuric acid in the presence of other brominated gases show the evolution of gaseous products including Br2O and Br2.

Iraci, Laura T.↗