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At least 37 records · Page 2

Flash photolysis resonance fluorescence investigation of the reaction of Cl/2P/ atoms with ClONO2

Rate constants for the removal of Cl(2P) atoms by homogeneous gas phase reaction with ClONO2 were measured using the flash photolysis resonance fluorescence technique at 224, 250, and 273 K. The values obtained have been used to derive the above Arrhenius equation. The uncertainties expressed are 95% confidence limits obtained using the statistical standard deviation of the individual rate constants plus a 15% additional estimated uncertainty attributed to difficulties in chlorine nitrate concentration measurements. The results indicate that destruction of chlorine nitrate by reaction with chlorine atoms is perhaps the least important of the atmospheric reactive channels, and is at least three orders of magnitude slower than calculated photodissociation rates at all stratospheric altitudes.

Kurylo, M. J.↗

A flash photolysis resonance fluorescence investigation of the reaction OH + CH3CCl3 yields H2O + CH2CCl3

The absolute rate constant for the reaction OH + CH3CCl3 yields H2O + CH2CCl3 was determined by the flash photolysis resonance fluorescence method from 253 to 363K. The use of the Arrhenius equation with atmospheric observational data on methyl chloroform nearly doubles the predicted tropospheric OH reaction sink strength for the removal of atmospheric gases whose lifetimes are controlled by OH. The increased use of methyl chloroform instead of the restricted trichloroethylene focused attention to its role in stratospheric ozone depletion, producing modeling analyses to determine the amount of released methyl chloroform which reaches the stratosphere. Since the primary atmospheric loss of CH3CCl3 is considered by reaction with OH radicals, these data are used to compute an average tropospheric OH concentration and the strength of the 'global tropospheric OH reaction sink'.

Kurylo, M. J.↗

Hydrogen and fluorine in the surfaces of lunar samples

The resonant nuclear reaction F-19 (p, alpha gamma)0-16 has been used to perform depth sensitive analyses for both fluorine and hydrogen in lunar samples. The resonance at 0.83 MeV (center-of-mass) in this reaction has been applied to the measurement of the distribution of trapped solar protons in lunar samples to depths of about 1/2 micrometer. These results are interpreted in terms of terrestrial H2O surface contamination and a redistribution of the implanted solar H which has been influenced by heavy radiation damage in the surface region. Results are also presented for an experiment to test the penetration of H2O into laboratory glass samples which have been irradiated with 0-16 to simulate the radiation damaged surfaces of lunar glasses. Fluorine determinations have been performed in a 1 pm surface layer on lunar samples using the same F-19 alpha gamma)0-16 resonance. The data are discussed from the standpoint of lunar fluorine and Teflon contamination.

Leich, D. A.↗

Hydrogen and fluorine in the surfaces of lunar samples

The resonant nuclear reaction F-19(p, alpha gamma)O-16 has been used to perform depth-sensitive analyses for both fluorine and hydrogen in lunar samples. The resonance at 0.83 MeV (center-of-mass) in this reaction has been applied to the measurement of the distribution of trapped solar protons in lunar samples to depths up to 0.45 microns. These results are interpreted in terms of terrestrial H2O surface contamination and of a redistribution of the implanted solar H which has been influenced by heavy radiation damage in the surface region. Results are also presented for an experiment to test the penetration of H2O into laboratory glass samples which have been irradiated with O-16 to simulate the radiation-damaged surfaces of lunar glasses. Fluorine determinations have been performed in a 1-micron surface layer on lunar samples using the same F-19(p, alpha gamma)O-16 resonance. The data are discussed from the standpoint that observed fluorine concentrations are a mixture of true lunar fluorine and Teflon contamination.

Leich, D. A.↗

A laser flash photolysis-resonance fluorescence kinetics study of the reaction Cl/2P/ + CH4 yields CH3 + HCl

The technique of laser flash photolysis-resonance fluorescence is employed to study the kinetics of the reaction Cl(2P) + CH4 yields CH3 + HCl over the temperature range 221-375 K. At temperatures less than or equal to 241 K the apparent bimolecular rate constant is found to be dependent upon the identity of the chemically inert gases in the reaction mixture. For Cl2/CH4/He reaction mixtures (total pressure = 50 torr) different bimolecular rate constants are measured at low and high methane concentrations. For Cl2/CH4/CCl/He and Cl2/CH4/Ar reaction mixtures, the bimolecular rate constant is independent of methane concentration, being approximately equal to the rate constant measured at low methane concentrations for Cl2/CH4/He mixtures. These rate constants are in good agreement with previous results obtained using the discharge flow-resonance fluorescence and competitive chlorination techniques. At 298 K the measured bimolecular rate constant is independent of the identity of the chemically inert gases in the reaction mixture and in good agreement with all previous investigations. The low-temperature results obtained in this investigation and all previous investigations can be rationalized in terms of a model which assumes that the Cl(2P 1/2) state reacts with CH4 much faster than the Cl(2P 3/2) state. Extrapolation of this model to higher temperatures, however, is not straightforward.

Ravishankara, A. R.↗

Flash photolysis resonance fluorescence investigation of the reaction of O /P-3/ atoms with ClONO2

The rate constant for the reaction of O (P-3) atoms with ClONO2 at 10 torr total pressure is assessed over the temperature range 225-273 K by the flash photolysis resonance fluorescence technique. The data, taken together with results given by Molina et al. (1977), have been used to formulate an Arrhenius expression suitable for stratospheric modeling applications. Comparison of the rate of ClONO2 destruction via the oxygen atom reaction with the solar photolysis rate shows that chemical reaction accounts for less than 15% of the CLONO2 removal at altitudes between 20 and 30 km.

Kurylo, M. J.↗

The depth distribution of hydrogen in lunar materials.

A technique employing the resonant nuclear reaction H-1(F-19, alpha gamma)O-16 has been used to measure hydrogen concentration versus depth in selected coarse fine fragments from the Apollo 11 and Apollo 15 missions, and in glass coated surface chips from two Apollo 15 rocks. The highly variable hydrogen content in the coarse fine fragments is concentrated mainly in a layer extending from the surface to a depth of 2000 plus or minus 500 A. The hydrogen content of the surface region of the Apollo 15 rock chips is comparable to that of the coarse fine samples, but is concentrated mainly within a few hundred angstroms of the surface. The hydrogen depth distribution in a piece of platinum foil from the Apollo 16 Lunar surface Cosmic Ray Experiment was also measured in an attempt to place a limit on the flux of 10- to 40-keV protons associated with a solar flare event.

Leich, D. A.↗

Quantitative multielement analysis using high energy particle bombardment

Charged particles ranging in energy from 0.8 to 4.0 MeV are used to induce resonant nuclear reactions, Coulomb excitation (gamma X-rays), and X-ray emission in both thick and thin targets. Quantitative analysis is possible for elements from Li to Pb in complex environmental samples, although the matrix can severely reduce the sensitivity. It is necessary to use a comparator technique for the gamma-rays, while for X-rays an internal standard can be used. A USGS standard rock is analyzed for a total of 28 elements. Water samples can be analyzed either by nebulizing the sample doped with Cs or Y onto a thin formvar film or by extracting the sample (with or without an internal standard) onto ion exchange resin which is pressed into a pellet.

Clark, P. J.↗

Quantitative multielement analysis using high energy particle bombardment

Charged particles ranging in energy from 0.8 to 4.0 MeV are used to induce resonant nuclear reactions, Coulomb excitation (gamma-rays), and X-ray emission in both thick and thin targets. Quantitative analysis is possible for elements from Li to Pb in complex environmental samples, although the matrix can severely reduce the sensitivity. It is necessary to use a comparator technique for the gamma-rays while for X-rays an internal standard can be used. A USGS standard rock is analyzed for a total of 28 elements. Water samples can be analyzed either by nebulizing the sample doped with Cs or Y a thin Formvar film or by extracting the sample onto ion exchange resin which is pressed into a pellet.

Clark, P. J.↗

Fluorine in meteorites

Microanalysis using a resonant nuclear reaction was used to measure F concentrations in USGS standard rocks and 21 meteorites. The F appears to be a moderately depleted element, but there were significant variations within each sample. Measurements on separated metal phases suggest that about 20% of meteoritic F is in the metal or in a phase closely associated with it. Simultaneous measurements of F, Mg, Na, Al and Si in the nonmagnetic fractions of meteorites suggest plagioclase as a F containing phase.

Allen, R. O., Jr.↗

Fluorine as a constituent in lunar magmatic gases

Fluorine surface deposits on Apollo 15 green glass, Apollo 17 orange glass, and on vesicle linings from Apollo 15 basalts were studied by a resonant nuclear reaction technique. Surface layers of about 10 to the 15th F atoms/sq cm were observed on unbroken spheroidal glass surfaces, whereas thinner (about 10 to the 14th atoms/sq cm) deposits were found on the vesicle linings.

Goldberg, R. H.↗