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Stief, L. J.

Publications and source records attributed to Stief, L. J..

At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS2002

Temperature Dependence of the Rate Constant for the CH3 Recombination Reaction: A Loss Process in Outer Planet Atmospheres

The methyl free radical (CH3) has been observed in the atmospheres of Saturn and Neptune by the ISO satellite. There are discrepancies between the column densities for the CH3 radical derived from the ISO observations and the column densities derived from atmospheric photochemical models. For Neptune the model column density is 1.5 times that derived from ISO. For Saturn the model is 6 times that from ISO. The recombination of methyl radicals is the major loss process for methyl in these atmospheres. The serious disagreement between observed and calculated levels of CH3 has led to suggestions that the atmospheric models greatly underestimated the loss of CH3 due to poor knowledge of the rate of the reaction (1) CH3 + CH3 + M goes to C2H6 + M at the low temperatures and pressures of these atmospheric systems. Although the reaction CH3 + CH3 + M goes to C2H6 + M has been extensively studied both theoretically and experimentally, the laboratory conditions have been, with only a few exceptions, higher temperatures (T greater than 298K), higher pressures (P greater than or equal to 10 Torr - 13.3 mbar) or M=Ar rather than H2 or He as the bath gas.

Cody, R. J.↗
NASA NTRS1995

The reaction O((3)P) + HOBr: Temperature dependence of the rate constant and importance of the reaction as an HOBr stratospheric loss process

The absolute rate constant for the reaction O((3)P) + HOBr has been measured between T = 233K and 423K using the discharge-flow kinetic technique coupled to mass spectrometric detection. The value of the rate coefficient at room temperature is (2.5 +/- 0.6) x 10(exp -11)cu cm/molecule/s and the derived Arrhenius expression is (1.4 +/- 0.5) x 10(exp -10) exp((-430 +/- 260)/T)cu cm/molecule/s. From these rate data the atmospheric lifetime of HOBr with respect to reaction with O((3)P) is about 0.6h at z = 25 km which is comparable to the photolysis lifetime based on recent measurements of the UV cross section for HOBr. Implications for HOBr loss in the stratosphere have been tested using a 1D photochemical box model. With the inclusion of the rate parameters and products for the O + HOBr reaction, calculated concentration profiles of BrO increase by up to 33% around z = 35 km. This result indicates that the inclusion of the O + HOBr reaction in global atmospheric chemistry models may have an impact on bromine partitioning in the middle atmosphere.

Nesbitt, F. L.↗
NASA NTRS1990

Role of the methylene amidogen (H2CN) radical in the atmospheres of Titan and Jupiter

The methylene amidogen (H2CN) radical can be shown to be an important intermediate in models for the formation of HCN (via N + CH3) and the recombination of H to H2 (via H + HCN) on Titan as well as in models for the formation of HCN (via NH2 + C2H3) in the atmosphere of Jupiter. Experiments in our laboratory in a discharge flow system with mass spectrometric detection of both reactants and products have established that the major product channel (90 percent for the reaction N + CH3 is that leading to H2CN + H. The same result was obtained for N + CD3 yields D2CN + D. The rate constant for the reaction D + D2CN yields DCN + D2 was measured for the first time and k(298 K) greater than 7 x 10(exp -11) cu cm/s was found. The same result was obtained for the H atom reaction. This is the final step in the reaction sequence leading to HCN on both Titan and Jupiter and to formation of H2 from H on Titan. The first measurement of the ionization potentials for H2CN and D2CN was also made. From electron impact studies I.P. = (9.6 + or - 1.0) eV was obtained for both radicals. An upperlimit of I.P. less than 11.6 eV came from observations of the H2CN radical by photoionization mass spectrometry using an Ar resonance lamp (106.7 nm). Further photoionization experiments are planned using synchrotron radiation plus monochromator as a tunable vacuum UV light source.

Nesbitt, F. L.↗
NASA NTRS1990

Upper atmosphere research: Reaction rate and optical measurements

The objective is to provide photochemical, kinetic, and spectroscopic information necessary for photochemical models of the Earth's upper atmosphere and to examine reactions or reactants not presently in the models to either confirm the correctness of their exclusion or provide evidence to justify future inclusion in the models. New initiatives are being taken in technique development (many of them laser based) and in the application of established techniques to address gaps in the photochemical/kinetic data base, as well as to provide increasingly reliable information.

Stief, L. J.↗
NASA NTRS1989

Branching ratios in the N + CH3 reaction - Formation of the methylene amidogen (H2CN) radical

The discharge-flow mass spectrometer system described by Brunning and Stief (1986) and Nejad et al. (1988) is used to determine the branching ratios for the reaction N + CH3. The results are presented in extensive tables and graphs and characterized in detail, and the implications for HCN formation in the atmosphere of Titan are considered. It is found that the main reaction channel at room temperature is H2CN + H, with about 10 percent giving HCN + H2; no isotope effects are seen when CH3 is replaced with CD3, and the branching ratios appear to be temperature-independent.

Marston, G.↗
NASA NTRS1987

Rate constant for the reaction of atomic oxygen with phosphine at 298 K

The rate constant for the reaction of atomic oxygen with phosphine has been measured at 298 K using flash photolysis combined with time-resolved detection of O(3P) via resonance fluorescence. Atomic oxygen was produced by flash photolysis of N2O or NO highly diluted in argon. The results were shown to be independent of (PH3), (O), total pressure and the source of O(3P). The mean value of all the experiments is k1 = (3.6 + or -0.8) x 10 to the -11th cu cm/s (1 sigma). Two previous measurements of k1 differed by more than an order of magnitude, and the results support the higher value obtained in a discharge flow-mass spectrometry study. A comparison with rate data for other atomic and free radical reactions with phosphine is presented, and the role of these reactions in the aeronomy or photochemistry of Jupiter and Saturn is briefly considered.

Stief, L. J.↗
NASA NTRS1986

Rate constant for the reaction of O(3P) with diacetylene from 210 to 423 K

The absolute rate constant for the reaction of O(3P) with diacetylene (C4H2) has been measured as a function of pressure and temperature by the flash-photolysis/resonance-fluorescence method. At 298 K and below, no pressure dependence of the rate constant was observed, but at 423 K a moderate (factor-of-2) increase was detected in the range 3 to 75 torr Ar.Results at or near the high-pressure limit are represented by an Arrhenius expression over the temperature range 210 to 423 K. The results are compared with previous determinations, all of which employed the discharge-flow/mass-spectrometry technique. The mechanism of the reaction is considered, including both primary and secondary processes. The heats of formation of the reactants, adducts, and products for the O(3P) + C4H2 reaction are discussed and contrasted with those for O(3P) + C2H2.

Mitchell, M. B.↗
NASA NTRS1986

Kinetic studies of the reaction of the SO radical with NO2 and ClO from 210 to 363 K

The rates of the reactions of the SO radical with NO2 and ClO (significant in the upper atmosphere of earth and Venus) were determined in a discharge flow system near 1 torr pressure with detection of radical and molecular species using collision-free sampling mass spectrometry. The rate constants were obtained from the decay of SO radicals in the presence of an excess of NO2 and ClO. The NO2 reaction was examined between 210 and 363 K and found to be temperature invariant: SO + NO2 yields SO2 + NO; k1 = (1.37 + or - 0.10) x 10 to the -11th cu cm/s. In addition, the ClO reaction was observed to be independent of temperature between 248 and 363 K: SO + ClO yields SO2 + Cl; k2 = (3.22 + or - 0.48) x 10 to the -11th cu cm/s. A comparison was made with previous investigations of these reactions at room temperature and with other radical-radical reactions involving SO or ClO.

Brunning, J.↗
NASA NTRS1986

The reaction H + C4H2 - Absolute rate constant measurement and implication for atmospheric modeling of Titan

The absolute rate constant for the reaction H + C4H2 has been measured over the temperature (T) interval 210-423 K, using the technique of flash photolysis-resonance fluorescence. At each of the five temperatures employed, the results were independent of variations in C4H2 concentration, total pressure of Ar or N2, and flash intensity (i.e., the initial H concentration). The rate constant, k, was found to be equal to 1.39 x 10 to the -10th exp (-1184/T) cu cm/s, with an error of one standard deviation. The Arrhenius parameters at the high pressure limit determined here for the H + C4H2 reaction are consistent with those for the corresponding reactions of H with C2H2 and C3H4. Implications of the kinetic carbon chemistry results, particularly those at low temperature, are considered for models of the atmospheric carbon chemistry of Titan. The rate of this reaction, relative to that of the analogous, but slower, reaction of H + C2H2, appears to make H + C4H2 a very feasible reaction pathway for effective conversion of H atoms to molecular hydrogen in the stratosphere of Titan.

Nava, D. F.↗
NASA NTRS1986

Reaction of atomic bromine with acetylene and loss rate of atmospheric acetylene due to reaction with OH, Cl, O, and Br

The first-order, diffusion, and bimolecular rate constants for the reaction Br + C2H2 yields C2H3Br are evaluated. The rate constants are measured at 210, 248, 298, and 393 K and at pressures between 15-100 torr Ar using flash photolysis combined with time-resolved detection of atomic bromine via Br resonance radiation. It is observed that the reaction is not affected by pressure or temperature and the bimolecular constant = (4.0 + or - 0.8) x 10 to the -15th cu cm/sec with an error of two standard deviations. The C2H2 + Br reaction rates are compared with reactions of C2H2 with Cl, OH, NH2, and H. The loss rates for atmospheric C2H2 for reactions with OH, Cl, O, and Br are calculated as a function of altitude.

Payne, W. A.↗
NASA NTRS1985

Pressure dependence of the absolute rate constant for the reaction Cl + C2H2 from 210-361 K

In recent years, considerable attention has been given to the role of chlorine compounds in the catalytic destruction of stratospheric ozone. However, while some reactions have been studied extensively, the kinetic data for the reaction of Cl with C2H2 is sparse with only three known determinations of the rate constant k3. The reactions involved are Cl + C2H2 yields reversibly ClC2H2(asterisk) (3a) and ClC2H2(asterisk) + M yields ClC2H2 + M (3b). In the present study, flash photolysis coupled with chlorine atomic resonance fluorescence have been employed to determine the pressure and temperature dependence of k3 with the third body M = Ar. Room temperature values are also reported for M = N2. The pressure dependence observed in the experiments confirms the expectation that the reaction involves addition of Cl to the unsaturated C2H2 molecule followed by collisional stabilization of the resulting adduct radical.

Brunning, J.↗
NASA NTRS1984

Temperature and pressure dependence of the absolute rate constant for the reactions of NH2 radicals with acetylene and ethylene

The absolute rate constants for the reaction between the NH2 free radical and acetylene and ethylene is measured experimentally using a flash photolysis technique. The constant is considered to be a function of temperature and pressure. At each temperature level of the experiment, the observed pseudo-first-order rate constants were assumed to be independent of flash intensity. The results of the experiment indicate that the bimolecular rate constant for the NH2 + C2H2 reaction increases with pressure at 373 K and 459 K but not at lower temperatures. Results near the pressure limit conform to an Arrhenius expression of 1.11 (+ or -) 0.36 x 10 to the -13th over the temperature range from 241 to 459 K. For the reaction NH2 + C2H4, a smaller rate of increase in the bimolecular rate constant was observed over the temperature range 250-465 K. The implications of these results for current theoretical models of NH2 + C2H2 (or H4) reactions in the atmospheres of Jupiter and Saturn are discussed.

Bosco, S. R.↗
NASA NTRS1983

The reaction NH2 + PH3 yields NH3 + PH2 - Absolute rate constant measurement and implication for NH3 and PH3 photochemistry in the atmosphere of Jupiter

The rate constant is measured over the temperature interval 218-456 K using the technique of flash photolysis-laser-induced fluorescence. NH2 radicals are produced by the flash photolysis of ammonia highly diluted in argon, and the decay of fluorescent NH2 photons is measured by multiscaling techniques. For each of the five temperatures employed in the study, the results are shown to be indepenent of variations in PH3 concentration, total pressure (argon), and flash intensity. It is found that the rate constant results are best represented for T between 218 and 456 K by the expression k = (1.52 + or - 0.16) x 10 to the -12th exp(-928 + or - 56/T) cu cm per molecule per sec; the error quoted is 1 standard deviation. This is the first determination of the rate constant for the reaction NH2 + PH3. The data are compared with an estimate made in order to explain results of the radiolysis of NH3-PH3 mixtures. The Arrhenius parameters determined here for NH2 + PH3 are then contrasted with those for the corresponding reactions of H and OH with PH3.

Bosco, S. R.↗
NASA NTRS1983

The reaction NH2 + PH3 yields NH3 + PH2: Absolute rate constant measurement and implication for NH3 and PH3 photochemistry in the atmosphere of Jupiter

The rate constant is measured over the temperature interval 218-456 K using the technique of flash photolysis-laser-induced fluorescence. NH2 radicals are produced by the flash photolysis of ammonia highly diluted in argon, and the decay of fluorescent NH2 photons is measured by multiscaling techniques. For each of the five temperatures employed in the study, the results are shown to be independent of variations in PH3 concentration, total pressure (argon), and flash intensity. It is found that the rate constant results are best represented for T between 218 and 456 K by the expression k = (1.52 + or - 0.16) x 10 to the -12th exp(-928 + or - 56/T) cu cm per molecule per sec; the error quoted is 1 standard deviation. This is the first determination of the rate constant for the reaction NH2 + PH3. The data are compared with an estimate made in order to explain results of the radiolysis of NH3-PH3 mixtures. The Arrhenius parameters determined here for NH2 + PH3 are then constrasted with those for the corresponding reactions of H and OH with PH3.

Bosco, S. R.↗
NASA NTRS1982

Rate constant for the reaction NH2 + NO from 216 to 480 K

The absolute rate constant was measured by the technique of flash photolysis-laser induced fluorescence (FP-LIF). NH2 radicals were produced by the flash photolysis of ammonia and the fluorescent NH2 photons were measured by multiscaling techniques. At each temperature, the results were independent of variations in total pressure, and flash intensity. The results are compared with previous determinations using the techniques of mass spectrometry, absorption spectroscopy, laser absorption spectroscopy, and laser induced fluorescence. The implications of the results are discussed with regard to combustion, post combustion, and atmospheric chemistry. The results are also discussed theoretically.

Stief, L. J.↗
NASA NTRS1981

A search for interstellar molecules in the spectra of highly reddened stars

A total of ten stars were observed with cameras of the International Ultraviolet Explorer (IUE) in both high and low dispersion. One star, X Persei (HD 24534, 6.0 BE), was analyzed in detail. Ultraviolet observations of the column densities of CO match those derived from the radio to within a factor of 4, with the difference probably due to the larger beam size of the radio measurement and the assumption of a thermal population in the rotational levels of CO. Upper limits are given to the log column densities for OH, HCl, and CH2 of 14.0, 12.3 and 12.8. The carbon abundance was found to be about solar with a possible depletion of about a factor of 2. With precautions concerning both noise and correct background, the IUE can be used for studies of interstellar molecules.

Lien, D.↗