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Kaufman, F.

Publications and source records attributed to Kaufman, F..

At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1985

Rates of elementary reactions - Measurement and applications

Techniques used for characterizing elementary chemical reaction kinetics are explored. Flash- or laser-photolysis (FP) involves producing reactive species on the psec time scale and monitoring the changes spectroscopically. In the discharge flow (DF) method, reactive species are produced continuously in a flow of an inert gas containing the reactants. FP avoids surface and transport effects, while DF allows several reactions to be studied in different regions of one flow. Transport and surface boundary layer models are defined for DF calculations and sample calculations are carried out to illustrate the difficulties inherent in theoretically defining the rate constants for elementary reactions. Applications of the models thus far derived in atmospheric science and combustion studies are discussed.

Kaufman, F.↗
NASA NTRS1985

Detailed course of the O + HO2 reaction

The elementary radical-radical reactions that are of such importance in laser, astrophysical, atmospheric, and combustion processes are increasingly open to direct rate measurement. Attention is presently given to the O + HO2 reaction, which has only one exothermic product channel: OH + O2. Isotopic product analysis was conducted spectroscopically using laser-induced fluorescence of OH. It is found that the simple atom-radical reaction takes place by way of the rapid formation and breakup of an unexpected radical intermediate, thereby raising questions as to the formation, thermochemistry, and decomposition of poorly known products in many other radical-radical reaction systems.

Sridharan, U. C.↗
NASA NTRS1985

Model predictions of ozone changes

The predictions of several one-dimensional models were examined for a number of prescribed scenarios in steady-state or time-dependent approximations. A small number of two-dimensional steady-state calculations for a limited number of scenarios were compared with the results of one-dimensional models. The sensitivity of the calculated predictions to the values of input parameters were examined in order to assess recognized uncertainties in these predictions.

Johnston, H. S.↗
NASA NTRS1981

Kinetics of the reaction OH + HO2 yields H2O + O2 at 296 K

The rate constant of the title reaction was measured in a discharge-flow reactor by addition of excess HO2 from a movable double injector to a gas stream containing small concentrations of OH. The concentration of OH was measured by laser-induced fluorescence, HO2 by conversion to OH, and H and O by vacuum-UV resonance fluorescence. Five sets of experiments, each with different excess concentration of HO2, gave an average rate constant of (7.5 + or - 1.2) x 10 to the -11th cu cm/s where the error limits (single sigma) include uncertainties of all experimental parameters. This result is compared with other findings and is discussed in terms of its importance in stratospheric chemistry and in rate theory.

Sridharan, U. C.↗
NASA NTRS1980

Kinetics of the reaction OH + H2O2 yields HO2 + H2O

The paper describes an experimental study of the title reaction that uses the discharge-flow technique, laser-induced-fluorescence detection of OH and simultaneous monitoring of O and H atoms in the 250-459 K range. The reaction is normal and free from surface effect interference in Teflon or halocarbon wax-coated tube, but not in clean Pyrex. OH radicals are generated in three ways and at low concentrations to eliminate side reactions. The rate constants were determined at 298 K and over the 250-459 K range, with a factor of two higher at 298 K and factors of 3 to 5 higher at 10 to 30 km altitude in the terrestrial atmosphere than previous studies have indicated. The effect of the higher rate constant on atmospheric processes and on recent laboratory measurements of other reactions is also discussed.

Sridharan, U. C.↗
NASA NTRS1979

Rates of the reactions of 1, 1, 1-trichloroethane /methyl chloroform/ and 1, 1, 2-trichloroethane with OH

Highly purified samples of the two chlorocarbons, trichloroethane and methyl chloroform, were reacted with OH over the temperature range of 278 to 460 K in a discharge-flow system with resonance flourescence detection of OH. Attention is given to the data obtained at various temperature levels and to the graph of Arrhenius' diagram. It is determined that the methyl chloroform reaction was slower and its temperature dependence somewhat steeper than the earlier measurements had indicated, probably due to the presence of faster reacting olefinic impurities in prior studies. Implications for stratospheric ozone reductions by C10-sub-x catalysis and for tropospheric OH-budget are briefly discussed.

Jeong, K.-M.↗
NASA NTRS1979

Chemical kinetic and photochemical data for use in stratospheric modelling

An evaluated set of rate constants and photochemical cross sections were compiled for use in modelling stratospheric processes. The data are primarily relevant to the ozone layer, and its possible perturbation by anthropogenic activities. The evaluation is current to, approximately, January, 1979.

Demore, W. B.↗
NASA NTRS1978

Upper bound and probable value of the rate constant of the reaction OH + HO2 yields H2O + O2

Discharge-flow experiments at 295 K of the OH + HO2 reaction are described in which excess O3 is added to OH through a movable injector; OH concentration is measured downstream by resonance fluorescence with and without addition of excess NO just upstream of the detector so that both OH concentration and OH concentration + HO2 concentration are determined independently. The data are compared with a computer model involving 12 reaction steps. A simple sensitivity analysis is carried out to establish how errors in the other 'known' rate constants affect the data fit. Best agreement is obtained between computer calculations and experiments when k1 for the OH + HO2 reaction is in the range 2-3 x 10 to the -11th cu cm/s. Values above about 5 x 10 to the -11th are very unlikely whereas those below about 1 x 10 to the -11th are less strongly excluded.

Chang, J. S.↗
NASA NTRS1977

Upper limits of the rate constants for the reactions of CFCl3/F-11/, CF2Cl2/F-12/, and N2O with OH - Estimates of corresponding lower limits to their tropospheric lifetimes

A discharge-flow system with resonance fluorescence detection of OH is used to study the reactions of CFCl3, CF2Cl2, and N2O with OH at temperatures up to 480 K. Little, if any reaction was found, with upper limits of 5, 6, and 4 x 10 to the -16th cu cm/s reported at 480 K for the three rate constants. A very simple model is used to calculate removal times exceeding 10,000 years for reaction with tropospheric OH.

Chang, J. S.↗
NASA NTRS1977

Kinetics of the reactions of ClO with O and with NO

The rate constants k1, k2, and k3 for the reactions Cl + O3 yields ClO + O2 (1), ClO + O yields Cl + O2 (2), and ClO + NO yields Cl + NO2 (3), respectively, were measured by the discharge-flow technique, in which chlorine atoms are added to a flow of O3 and either O or NO in a helium carrier gas. The conditions of the experiment were such that the steady-state concentration ratios of Cl to ClO are simply interpretable in terms of the rate constant ratios k2/k3 or k3/k1. These rate constant ratios were measured over the range 220 to 298 K and combined with the directly determined k1 value to yield k2 and k3. The results are: k1 = 2.12 x 10 to the -11th exp(-157/T); k2 = 3.38 x 10 to -11th exp(75 plus or minus 40/T); and k3 = 1.13 x 10 to the -11th exp(200 plus or minus 30/T) cu cm/sec.

Zahniser, M. S.↗
NASA NTRS1977

Apollo-Soyuz O/3P/ and N/4S/ density measurement by UV spectroscopy

The densities of O(3P) and N(4S) at 225 km were determined during the Apollo-Soyuz Test Project by a resonance absorption-fluorescence technique in which O I and N I line radiation produced and collimated on board the Apollo was reflected from the Soyuz back to the Apollo for spectral analysis. The two spacecraft maneuvered so that a range of observation angles of plus or minus 25 deg with respect to the normal to the orbital velocity vector was scanned. The measurements described were made at night on two consecutive orbits at spacecraft separations of 150 and 500 m. The results indicate an O density of 1.15 billion per cu cm (plus or minus 30%), agreeing with mass-spectrometric measurements made under similar conditions, and an N density of 5.6 to 11.2 million per cu cm, in good agreement with recent measurements but suggesting a smaller diurnal variation than predicted by present models.

Donahue, T. M.↗
NASA NTRS1977

Ultraviolet absorption: Experiment MA-059

A technique devised to permit the measurement of atmospheric species concentrations is described. This technique involves the application of atomic absorption spectroscopy and the quantitative observation of resonance fluorescence in which atomic or molecular species scatter resonance radiation from a light source into a detector. A beam of atomic oxygen and atomic nitrogen resonance radiation, strong unabsorbable oxygen and nitrogen radiation, and visual radiation was sent from Apollo to Soyuz. The density of atomic oxygen and atomic nitrogen between the two spacecraft was measured by observing the amount of resonance radiation absorbed when the line joining Apollo and Soyuz was perpendicular to their velocity with respect to the ambient atmosphere. Results of postflight analysis of the resonance fluorescence data are discussed.

Donahue, T. M.↗
NASA NTRS1976

Ultraviolet absorption experiment MA-059

The ultraviolet absorption experiment performed during the Apollo Soyuz mission involved sending a beam of atomic oxygen and atomic nitrogen resonance radiation, strong unabsorbable oxygen and nitrogen radiation, and visual radiation, all filling the same 3 deg-wide field of view from the Apollo to the Soyuz. The radiation struck a retroreflector array on the Soyuz and was returned to a spectrometer onboard the Apollo. The density of atomic oxygen and atomic nitrogen between the two spacecraft was measured by observing the amount of resonance radiation absorbed when the line joining Apollo and Soyuz was perpendicular to their velocity with respect to the ambient atmosphere. Information concerning oxygen densities was also obtained by observation of resonantly fluorescent light. The absorption experiments for atomic oxygen and atomic nitrogen were successfully performed at a range of 500 meters, and abundant resonance fluorescence data were obtained.

Donahue, T. M.↗
NASA NTRS1976

The O(3P) and N(4S) density measurement at 225 km by ultraviolet absorption and fluorescence in the Apollo-Soyuz test project

The densities of O(3P) and N(4S) at 225 km were determined during the Apollo Soyuz Test Project by a resonance absorption/fluorescence technique in which OI and NI line radiation produced and collimated on board the Apollo was reflected from the Soyuz back to the Apollo for spectral analysis. The two spacecraft maneuvered so that a range of observation angles of plus or minus 15 deg with respect to the normal to the orbital velocity vector was scanned. The measurements were made at night on two consecutive orbits at spacecraft separations of 150 and 500 m. The resulting relative counting rates as function of observation angle were compared to calculated values to determine the oxygen value. This value agrees with mass spectrometric measurements made under similar conditions. The nitrogen value is in good agreement with other measurements and suggests a smaller diurnal variation than is predicted by present models.

Kaufman, F.↗
NASA NTRS1975

Kinetics of the reaction OH + D yields OD + H

The reaction of OH radicals with D-atoms to form OD has been studied at room temperature in a discharge-flow system utilizing UV resonance fluorescence detection of the molecular species. A rate constant of approximately 1.3 by 10 to the -10th power cu cm per sec is reported where the error limits include systematic error estimates. Astrophysical and kinetic implications are discussed briefly.

Margitan, J. J.↗