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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 289 records · Page 16
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NASA NTRS1985

Laboratory studies on the reactions between chlorine, sulfur dioxide, and oxygen - Implications for the Venus stratosphere

Fourier transform IR spectrophotometry is used to monitor the reactants and products in a Venus stratosphere simulation study involving the photolysis of mixtures of Cl2 and SO2, with and without O2 present in an atmosphere of N2. When several speculative reactions inferred from these experiments are incorporated by the Yung and DeMore (1982) model of Venus stratospheric chemistry, it emerges that SO2Cl2 is a key reservoir species for chlorine, and that the reaction between Cl and SO2 furnishes an important cycle for the destruction of O2 and the conversion of SO2 to H2SO4, thereby providing a possible solution to the photochemistry of the Venus stratosphere.

Demore, W. B.↗
NASA NTRS1986

Observation of several chlorine nitrate (ClONO2) bands in stratospheric infrared spectra

Four of the most prominent and sharpest infrared absorption features of chlorine nitrate at 780.2, 807.7, 809.4, and 1292.6/cm have been observed in a series of infrared solar spectra obtained at an unapodized spectral resolution of 0.01/cm, using the Atmospheric Trace Molecule Spectroscopy instrument from on-board Sapcelab 3. A quantitative analysis of the nu4 Q branch at 780.2/cm has provided insight into the concentration of ClONO2 between 19 and 40 km altitude. While the mean profile deduced from three sunset occultations near 30 deg N latitude exhibits a shape close to that predicted by model calculations, its concentrations in the 20 to 32 km altitude range are, however, about 30 percent larger, reaching a peak concentration of 9 x 10 to the 8th molecules/cu cm at 25 km. The concentrations above 32 km, deduced from one sunrise occultation at 47 deg JS, are even larger than the corresponding sunset values at 30 deg N latitude. Some of these discrepancies may be caused by the rather large uncertainty in the assumed Q branch strength.

Zander, R.↗
NASA NTRS1986

Reactions of chlorine nitrate with HCl and H2O

The kinetics of the reactions of chlorine nitrate with HCl and H2O are characterized using a static photolysis/Fourier transform infrared spectrophotometer apparatus. For the homogeneous gas-phase reaction with HCl, an upper limit for the rate constant of less than 8.4 x 10 to the -21st, and for the reaction with H2O, a limit of less than 3.4 x 10 to the -21st cu cm/molecule per s, were obtained at 296 + or - 2 K. The yield of HNO3 is almost unity in both cases, and no synergistic effect is noted between HCl and H2O. The kinetic behavior of the reaction with H2O is well described by simple first-order kinetics, while the behavior of the reaction with HCl is described in terms of the Langmuir adsorption isotherm.

Hatakeyama, Shiro↗
NASA NTRS1987

The use of atmospheric measurements to constrain model predictions of ozone change from chlorine perturbations

Atmospheric photochemistry models have been used to predict the sensitivity of the ozone layer to various perturbations. These same models also predict concentrations of chemical species in the present day atmosphere which can be compared to observations. Model results for both present day values and sensitivity to perturbation depend upon input data for reaction rates, photodissociation rates, and boundary conditions. A method of combining the results of a Monte Carlo uncertainty analysis with the existing set of present atmospheric species measurements is developed. The method is used to examine the range of values for the sensitivity of ozone to chlorine perturbations that is possible within the currently accepted ranges for input data. It is found that model runs which predict ozone column losses much greater than 10 percent as a result of present fluorocarbon fluxes produce concentrations and column amounts in the present atmosphere which are inconsistent with the measurements for ClO, HCl, NO, NO2, and HNO3.

Douglass, Anne R.↗
NASA NTRS1988

Submillimeter measurement of stratospheric chlorine monoxide

The measurement of the ClO concentration in the stratosphere provides crucial information on the mechanism for ozone depletion by catalytic reactions involving chlorine. Two rotational transitions of ClO, J = 35/2 - 33/2 and J = 37/2 - 35/2 have been identified in balloon-borne high-resolution spectra of the stratospheric emission in the submillimeter region. The measurements provide information on the ClO concentration at altitudes around 28 km. In the case of afternoon measurements obtained in April 1979, a scaling factor of 0.85 (+0.67, -0.64) is observed, and in the case of afternoon and early morning measurements obtained in October 1982, a scaling factor of 0.88 (+0.18, -0.08) is observed.

Carli, B.↗
NASA NTRS1988

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.↗
NASA NTRS1988

Thermochemical stabilities and vibrational spectra of isomers of the chlorine oxide dimer

Molecular orbital calculations were performed to determine the relative thermochemical stabilities and IR vibrational spectra of isomers of the ClO dimer. Two straight-chain isomers (ClOOCl and ClOClO) and one branched species (ClClO2) were identified as energy minima on the Cl2O2 potential surface. It is shown that ClOOCl and ClClO2 are comparable in terms of stability, while ClOClO is about 11 kcal/mol higher in energy. The IR spectra obtained by Molina and Molina (1987) as a result of the reaction of chlorine atoms with ClO precursors are consistent with the production of the two most stable forms of Cl2O2.

Mcgrath, M. P.↗
NASA NTRS1988

Reactions of silicon-based ceramics in mixed oxidation chlorination environments

The reaction of silicon-based ceramics with 2 percent Cl2/Ar and 1 percent Cl2/1 percent to 20 percent O2/Ar at 950 C was studied with thermogravimetric analysis and high-pressure mass spectrometry. Pure Si, SiO2, several types of SiC, and Si3N4 were examined. The primary corrosion products were SiCl4(g) and SiO2(s) with smaller amounts of volatile silicon oxychlorides. The reactions appear to occur by chlorine penetration of the SiO2 layer, and gas-phase diffusion of the silicon chlorides away from the sample appears to be rate limiting. Pure SiO2 shows very little reaction with Cl2, SiC with excess Si is more reactive than the other materials with Cl2, whereas SiC with excess carbon is more reactive than the other materials with Cl2/O2. Si3N4 shows very little reaction with Cl2. These differences are explained on the basis of thermodynamic and microstructural factors.

Marra, John E.↗
NASA NTRS1989

Nitrogen and chlorine species in the spring Antarctic stratosphere - Comparison of models with Airborne Antarctic Ozone Experiment observations

The concentrations and the time development of chlorine and nitrogen trace gases in the Antarctic stratosphere before, during, and after the Airborne Antractic Ozone Experiment (AAOE) were simulated using photochemical models of the Antractic stratosphere during winter/spring. The initial conditions in the calculations were constrained using observations by the AAOE instrument. The comparison of calculated results with the AAOE measurements of HCl and ClO suggest that heterogeneous chemistry was maintained throughout the month of September 1987.

Rodriguez, J. M.↗
NASA NTRS1990

The role of chlorine chemistry in Antarctic ozone loss - Implications of new kinetic data

New kinetic data yielding a slower formation rate and larger absorption cross sections of Cl2O2 are incorporated into a photochemical model to reassess the role of chlorine chemistry in accounting for the ozone reductions derived from TOMS observations in different regions of the Antarctic polar vortex during 1987. The model is further constrained by existing measurements from the Airborne Antarctic Ozone Experiment and the National Ozone Expedition II. Calculated concentrations of ClO based on the new kinetic data increase by almost a factor of two between the collar and core regions of the vortex during the second half of September. The calculated ozone reductions in the vortex core appear to be consistent with the TOMS observations in spite of the slower rate for the self-reaction of ClO.

Rodriguez, Jose M.↗
NASA NTRS1991

Simulation of the present-day atmospheric ozone, odd nitrogen, chlorine and other species using a coupled 2-D model in isentropic coordinates

A zonally averaged two-dimensional model for chemical species in the atmosphere (Olaguer et al., 1990), with coupled dynamics, radiation transfer, and chemistry, is used to study the present-day atmospheric ozone, odd nitrogen, chlorine, other species. The model utilizes all zonally averaged physical equations of momentum, energy, and mass and determines self-consistently the advective and diffusive tranasport parameters from the temperature specific to the period of observation. A comparison of the model results with observations showed good agreement.

Yang, H.↗
NASA NTRS1992

The chlorine budget of the present-day atmosphere - A modeling study

The contribution of source gases to the total amount of inorganic chlorine (ClY) is examined analytically with a time-dependent model employing 11 source gases. The source-gas emission data are described, and the modeling methodology is set forth with attention given to the data interpretation. The abundances and distributions are obtained for all 11 source gases with corresponding ClY production rates and mixing ratios. It is shown that the ClY production rate and the ClY mixing ratio for each source gas are spatially dependent, and the change in the relative contributions from 1950 to 1990 is given. Ozone changes in the past decade are characterized by losses in the polar and midlatitude lower stratosphere. The values for CFC-11, CCl4, and CH3CCl3 suggest that they are more evident in the lower stratosphere than is suggested by steady-state estimates based on surface concentrations.

Weisenstein, Debra K.↗
NASA NTRS1991

Future chlorine-bromine loading and ozone depletion

The prediction of future ozone requires three elements: (1) a scenario for the net emissions of chemically and radiatively active trace gases from the land and oceans; (2) a global atmospheric model that projects the accumulation of these gases; and (3) a chemical transport model that describes the distribution of ozone for a prescribed atmospheric composition and climate. This chapter, of necessity, presents models for all three elements and focuses on the following: (1) atmospheric abundance of chlorine and bromine in the form of halocarbons; and (2) the associated perturbations to stratospheric ozone.

Prather, Michael J.↗
NASA NTRS1992

Direct observation of ClO from chlorine nitrate photolysis

Chlorine nitrate photolysis has been investigated with the use of a molecular beam technique. Excitation at both 248 and 193 nanometers led to photodissociation by two pathways, ClONO2 yields ClO + NO2 and ClONO2 yields Cl + NO3, with comparable yields. This experiment provides a direct measurement of the ClO product channel and consequently raises the possibility of an analogous channel in ClO dimer photolysis. Photodissociation of the ClO dimer is a critical step in the catalytic cycle that is presumed to dominate polar stratospheric ozone destruction. A substantial yield of ClO would reduce the efficiency of this cycle.

Minton, Timothy K.↗
NASA NTRS1992

Temperature dependence and mechanism of the reaction between O(3P) and chlorine dioxide

Second-order rate constants for the decay of O(3P) in excess chlorine dioxide, k(II), were measured as a function of total pressure (20-600 Torr argon) and temperature (248-312 K), using flash photolysis-atomic resonance fluorescence. Results indicate that k(II) is pressure dependent with a value, K(b), that is nonzero at zero pressure, and both the third-order rate constant and k(b) have negative temperature dependences.

Colussi, A. J.↗
NASA NTRS1995

Cleaning without chlorinated solvents

Because of health and environmental concerns, many regulations have been passed in recent years regarding the use of chlorinated solvents. The Oak Ridge Y-12 Plant has had an active program to find alternatives for these solvents used in cleaning applications for the past 7 years. During this time frame, the quantity of solvents purchased has been reduced by 92 percent. The program has been a twofold effort. Vapor degreasers used in batch cleaning operations have been replaced by ultrasonic cleaning with aqueous detergent, and other organic solvents have been identified for use in hand-wiping or specialty operations. In order to qualify these alternatives for use, experimentation was conducted on cleaning ability as well as effects on subsequent operations such as welding, painting, and bonding. Cleaning ability was determined using techniques such as x-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) which are capable of examining monolayer levels of contamination on a surface. Solvents have been identified for removal of rust preventative oils, lapping oils, machining coolants, lubricants, greases, and mold releases. Solvents have also been evaluated for cleaning urethane foam spray guns, swelling of urethanes, and swelling of epoxies.

Thompson, L. M.↗
NASA NTRS1994

The distribution of hydrogen, nitrogen, and chlorine radicals in the lower stratosphere: Implications for changes in O3 due to emission of NO(y) from supersonic aircraft

In situ measurements of hydrogen, nitrogen, and chlorine radicals obtained in the lower statosphere during SPADE are compared to results from a photochemical model that assimilates measurements of radical precursors and environmental conditions. Models allowing for heterogeneous hydrolysis of N2O5 agree well with measured concentrations of NO and ClO, but concentrations of HO2 and OH are underestimated by 10 to 25%, concentrations of NO2 are overestimated by 10 to 30%, and concentrations of HCl are overestimated by a factor of 2. Discrepancies for (OH) and (HO2) are reduced if we allow for higher yields of O((1)D) from O2 photolysis and for heterogeneous production of HNO2. The data suggest more efficent catalytic removal of O3 by hydrogen and halogen radicals relative to nitrogen oxide radicals than predicted by models using recommendend rates and cross sections. Increased in (O3) in the lower stratosphere may be larger in response to inputs of NO(y) from supersonic aircraft than estimated by current assessment models.

Salawitch, R. J.↗
NASA NTRS1994

The diurnal variation of hydrogen, nitrogen, and chlorine radicals: Implications for the heterogeneous production of HNO2

In situ measurements of hydrogen, nitrogen, and chlorine radicals obtained through sunrise and sunset in the lower statosphere during SPADE are compared to results from a photochemical model constrained by observed concentrations of radical precursors and environmental conditions. Models allowing for heteogeneous hydrolysis of N2O5 on sulfate aerosols agree with measured concentrations of NO, NO2, and ClO throughout the day, but fail to account for high concentrations of OH and HO2 observed near sunrise and sunset. The morning burst of (OH) and (HO2) coincides with the rise of (NO) from photolysis of NO2, suggesting a new source of HO(x) that photolyzes in the near UV (350 to 400 nm) spectral region. A model that allow for the heterogeneous production of HNO2 results in an excellent simulation of the diurnal variations of (OH) and (HO2).

Salawitch, R. J.↗