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At least 163 records · Page 9

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NASA NTRS1979

High temperature electrolytic recovery of oxygen from gaseous effluents from the carbo-chlorination of lunar anorthite and the hydrogenation of ilmenite: A theoretical study

A thermodynamic analysis discusses the compositions of gaseous effluents from the reaction of carbon and chlorine and of hydrogen with lunar anorthite and ilmenite, respectively. The computations consider the effects of the indigenous volatiles on the solid/gas reactions and on the composition of the effluent gases. A theoretical parameterization of the high temperature electrolysis of such gases is given for several types of solid ceramic electrolytes, and the effect of oxygen removal on the effluents is computed. Potential chemical interactions between the gases and the ceramic electrolytes are analyzed and discussed.

Erstfield, T. E.↗

NASA NTRS1979

The photolysis of chlorine in the presence of ozone, nitric acid and nitrogen dioxide

The following three systems were investigated: the Cl2-O3 system, the Cl2-O2-NO system and the Cl2-NO2-M system. In the first system, the reaction between ClO and O3, the reaction between OClO and O3, and the mechanism of the Cl2-O3 system were studied. In the second system, the reaction between ClOO and NO was investigated. In the last system, the reaction between Cl and NO2 was investigated as well as the kinetics of the chemiluminescence of the Cl-NO2-O3 reaction. In the first system, Cl2 was photolyzed at 366 nm in the presence of O3 within the temperature range 254-297 K. O3 was removed with quantum yields of 5.8 + or - 0.5, 4.0 + or - 0.3, 2.9 + or - 0.3 and 1.9 + or - 0.2 at 297, 283, 273, and 252 K respectively, invariant to changes in the initial O3 or Cl2 concentration, the extent of conversion or the absorbed intensity, I sub a. The addition of nitrogen had no effect on -phi(03). The Cl2 removal quantum yields were 0.11 + or - 0.02 at 297 K for Cl2 conversions of about 30%, much higher than expected from mass balance considerations based on the initial quantum yield of 0.089 + or - 0.013 for OClO formation at 297 K. The final chlorine-containing product was Cl2O7. It was produced at least in part through the formation of OClO as an intermediate which was also observed with an initial quantum yield of phi sub i(OClO) = 2500 exp(-(3025 + or - 625)/T) independent of (O3) or I sub a.

Stuper, W. W.↗

NASA NTRS1979

Rate constant for the reaction of atomic chlorine with formaldehyde from 200 to 500 K

The absolute rate constant for the reaction of atomic chlorine with formaldehyde has been measured from 200 to 500 K using the flash photolysis-resonance fluorescence technique. The results were independent of substantial variations in (H2CO), total pressure (Ar), and flash intensity (i.e., initial (Cl)). The rate constant was shown to be invariant with temperature, the best representation for this temperature range being k-sub-1 = (7.48 + or - 0.50) times 10 to the -11 cu cm/molecule sec, where the error is one standard deviation. This result is compared with the only previous determination of k-sub-1, which was a relative value obtained at 298 K. The rate constant is theoretically discussed, and the potential importance of the reaction in stratospheric chemistry is considered.

Michael, J. V.↗

NASA NTRS1980

Absolute rate constant of the reaction between chlorine /2P/ atoms and hydrogen peroxide from 298 to 424 K

The absolute rate constant of the reaction between chlorine (2P) atoms and hydrogen peroxide was determined from 298 to 424 K, using the discharge flow resonance fluorescence technique. Pseudo-first-order conditions were used with hydrogen peroxide in large excess. A fast flow-sampling procedure limited hydrogen peroxide decomposition to less than 5% over the temperature range studied. At 298 K, the rate constant is (4.1 plus or minus 0.2) x 10 to the minus 13th cu cm/molecule-sec.

Keyser, L. F.↗

NASA NTRS1980

Chlorine chemistry in diffuse interstellar clouds

The results of recent observations of the column densities of chlorine species in diffuse interstellar clouds are inconsistent with the column densities predicted by model calculations. The use of new atomic and molecular data fails to decrease the discrepancy. It is speculated that the exothermic reaction Cl(+) yields HCl(+) + H may not be rapid at the low temperatures prevailing in diffuse interstellar clouds.

Black, J. H.↗

NASA NTRS1982

Coal desulfurization by aqueous chlorination

A method of desulfurizing coal is described in which chlorine gas is bubbled through an aqueous slurry of coal at low temperature below 130 degrees C., and at ambient pressure. Chlorinolysis converts both inorganic and organic sulfur components of coal into water soluble compounds which enter the aqueous suspending media. The media is separated after chlorinolysis and the coal dechlorinated at a temperature of from 300 C to 500 C to form a non-caking, low-sulfur coal product.

Kalvinskas, J. J.↗

NASA NTRS1983

Infrared heterodyne spectroscopy of seven gases in the vicinity of chlorine monoxide lines

Chlorine monoxide (ClO) is thought to play an important role in a photochemical cycle which causes the destruction of ozone in the earth's stratosphere. Since lines of the (1,0) fundamental of ClO lie near C-14O2-16, laser lines, IR heterodyne spectroscopy is potentially an important technique for monitoring the ClO abundance. However, due to the presence of lines from other trace atmospheric gases in this spectral range, the interpretation of such observations is ambiguous unless high resolution laboratory measurements support the identifications. Measured frequencies are reported for spectral lines of seven trace atmospheric gases which absorb near the C-14O2-16 laser transitions relevant to the detection of ClO by IR heterodyne spectroscopy.

Weaver, H. A.↗

NASA NTRS1985

The isotopic composition of cosmic ray chlorine

The isotopic composition of galactic cosmic ray chlorine (approx. = 225 MeV/amu) has been studied using the high energy cosmic ray experiment on the International Sun Earth Explorer 3 (ISEE-3) spacecraft. The abundances of 35C1 and 37C1 are found to be consistent with the secondary production expected from a propagation model developed to account for both light and subiron secondaries. An upper limit on the abundance of the radioactive isotope 36C1 (halflife approx. = 0.3 Myr) is used to set a lower limit on the confinement time of cosmic rays of approximately 1 Myr.

Wiedenbeck, M. E.↗

NASA NTRS1985

Chlorine in dense interstellar clouds - The abundance of HCl in OMC-1

The first detection of a chlorine-bearing molecular species in the interstellar medium via emission from the J = 1-0 transition of HCl at 625.9 GHz toward OMC-1 is reported. The relative strengths, widths, and velocities of the resolved hyperfine components are consistent with moderate optical depth emission originating from dense, quiescent molecular cloud material. The overall emission strength implies a fractional abundance of f(HCl/H2) of about (0.5-5.0) x 10 to the -8th, depending on the density of the emitting region. This is approximately an order of magnitude below previous theoretical estimates and a factor of 3-30 below the cosmic abundance of Cl. Recent laboratory work suggests that the lowered fractional abundance of HCl is caused by a combination of depletion onto grains with gas-phase loss processes such as the reaction of HCl with C(+).

Blake, G. A.↗

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.↗