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Michael, J. V.

Publications and source records attributed to Michael, J. V..

At least 19 records
All sourcesNASA NTRSDOE OSTI
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

Temperature dependence of the NO + O3 reaction rate from 195 to 369 K

The temperature dependence of the NO + O3 reaction rate was examined by means of the fast flow technique. Several different experimental conditions and detection schemes were employed. With excess NO or excess O3, NO2 chemiluminescence was monitored. In addition, with excess O3, NO was followed by fluorescence induced by an NO microwave discharge lamp. The results of the three independent sets of data are compared and found to agree within experimental error, indicating the absence of secondary chemistry which might complicate the kinetics. The data exhibit curvature on an Arrhenius plot; however, the simple Arrhenius expression k = (2.6 + or - 0.8) x 10 to the -12th exp(-1435 + or - 64/T) cu cm/molecule s is an adequate description for T between 195 and 369 K. This result is compared to earlier determinations.

Michael, J. V.↗
NASA NTRS1980

Pressure dependence of the absolute rate constant for the reaction OH + C2H2 from 228 to 413 K

The pressure dependence of the absolute rate constant for the reaction of the hydroxyl radical with acetylene, important in both atmospheric and combustion chemistry, is determined for temperatures between 228 and 413 K. The flash photolysis-resonance fluorescence technique was employed at five temperatures over wide ranges of pressure and acetylene concentrations, with the OH produced by water photolysis and hydroxyl resonance fluorescent photons measured by multiscaling techniques. Results indicate that, except at the lowest temperature, the bimolecular rate constant for the reaction depends strongly on total pressure, with the pressure effect becoming more pronounced with increasing temperature. At limiting high pressures, the rate constant is found to be equal to 6.83 + or - 1.19 x 10 to the -12th exp (-646 + or - 47/T) cu cm/molecule per sec, where T is the temperature. Results thus demonstrate the importance of environmental conditions in theoretical studies of atmospheric and combustion product compositions

Michael, J. V.↗
NASA NTRS1980

Rate constant for the reaction of hydroxyl radical with formaldehyde over the temperature range 228-362 K

Absolute rate constants for the reaction OH + H2CO have been measured over the temperature range 228-362 K using the flash photolysis-resonance fluorescence technique. The results were independent of variations in forbidden H2CO, total pressure of forbidden Ar and flash intensity (i.e., initial forbidden OH). The rate constant was found to be invariant with temperature in this range, the best representation being k1 = (1.05 + or - 0.11) x 10 to the -11th cu cm/molecule sec where the error is two standard deviations. This result is compared with previous absolute and relative determinations of k1. The reaction is also discussed from a theoretical point of view.

Stief, L. J.↗
NASA NTRS1980

Pressure dependence of the absolute rate constant for the reaction OH + C2H2 from 228 to 413K

The pressure dependence of absolute rate constants for the reaction of OH + C2H2 yields products has been examined at five temperatures ranging from 228 to 413 K. The experimental techniques which was used is flash photolysis-resonance fluoresence. OH was produced by water photolysis and hydroxyl resonance fluorescent photons were measured by multiscaling techniques. The results indicate that the low pressure bimolecular rate constant is 4 x 10 the the minus 13th power cu cm molecule (-1) s(-1) over the temperature range studied. A substantial increase in the bimolecular rate constant with an increase in pressure was observed at all temperatures except 228 K. This indicates the importance of initial adduct formation and subsequent stablization. The high pressure results are well represented by the Arrhenius expression (k sub bi) sub infinity = (6.83 + or - 1.19) x 10 to the minus 12th power exp(-646 + or - 47/T)cu cm molecule (-1) s(-1). The results are compared to previous investigated and are theoretically discussed. The implications of these results on modeling of terrestrial and planetary atmospheres and also in combustion chemistry are discussed.

Michael, J. V.↗
NASA NTRS1980

Rate constant for the reaction of hydroxyl radical with formaldehyde over the temperature range 228-362 K

Absolute rate constants for the reaction OH ? H2CO measured over the temperature range 228-362 K using the flash photolysis-resonance fluorescence technique are given. The results are independent of variations in H2CO concentration, total pressure Ar concentration, and flash intensity (i.e., initial OH concentration). The rate constant is found to be invariant with temperature in this range, the best representation being k sub 1 = (1.05 ? or - 0.11) x 10 to the 11th power cu cm molecule(-1) s(-1) where the error is two standard deviations. This result is compared with previous absolute and relative determinations of k sub 1. The reaction is also discussed from a theoretical point of view.

Stief, L. J.↗
NASA NTRS1979

Rate constant for the reaction H + NO2 from 195 to 400 K with FP-RF and DF-RF techniques

Measurements are made of the rate constant for the reaction H + NO2 yielding OH + NO over significant temperature ranges with the flash photolysis-resonance fluorescence (FP-RF) technique and also with the discharge flow-resonance fluorescence (DF-RF) technique. Since it is important to study chemical reactions with more than one technique, the above reaction is investigated with the FP-RF technique over the temperature range 230-400 K. The results reported do not agree with earlier determinations. Accordingly, a separate set of measurements is made with the DF-RF technique over the temperature range 195-368 K; the results are also reported. The reaction is also considered theoretically, especially with regard to the question of temperature dependence and absolute magnitude of the rate constant.

Michael, J. V.↗
NASA NTRS1979

Absolute rate constants for the reaction of atomic hydrogen with ketene from 298 to 500 K

Rate constants for the reaction of atomic hydrogen with ketene have been measured at room temperature by two techniques, flash photolysis-resonance fluorescence and discharge flow-resonance fluorescence. The measured values are (6.19 + or - 1.68) x 10 to the -14th and (7.3 + or - 1.3) x 10 to the -14th cu cm/molecule/s, respectively. In addition, rate constants as a function of temperature have been measured over the range 298-500 K using the FP-RF technique. The results are best represented by the Arrhenius expression k = (1.88 + or - 1.12) x 10 to the -11th exp(-1725 + or - 190/T) cu cm/molecule/s, where the indicated errors are at the two standard deviation level.

Michael, J. V.↗
NASA NTRS1979

The reaction N/4S/ + O3 - An upper limit for the rate constant at 298 K

The reaction of N(4S) atoms with ozone was examined at 298 K using discharge flow and flash photolysis techniques, both coupled with resonance fluorescence detection of N(4S). No reaction was detected in either system, and an upper limit of 5 x 10 to the -16th cu cm/molecule/s was estimated for the rate constant. This is 1000 times lower than the presently accepted value of 5.7 x 10 to the -13th cu cm/molecule/s which is based on a discharge flow-mass spectrometric study of the reaction. Potential complications in the latter experiment are discussed.

Stief, L. J.↗
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 NTRS1978

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

A flash photolysis - resonance fluorescence technique was used to measure rate constant. 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 = (7.48 + or - 0.50) x 10 to the minus 11 power cu cm molecule-1 s-1 where the error is one standard deviation. The rate constant is theoretically discussed and the potential importance of the reaction in stratospheric chemistry is considered.

Michael, J. V.↗
NASA NTRS1978

The reaction Cl + H2CO yields HCl + HCO: Decreased sensitivity of stratospheric ozone to chlorine perturbations

The absolute rate constant for the reaction Cl + H2CO yields HCl + HCO has been determined by the flash-photolysis-resonance fluorescence method to be + or - 0.9 (2 sigma) x 10 to the -11th power cu cm/molecule per sec at 298 K and to have a negligible temperature dependence. This rate, which at stratospheric temperatures is more than 2000 times faster than the rate of Cl + CH4 and more than a factor of 2 faster than Cl + HO2, indicates that formaldehyde (H2CO) will compete significantly with methane (CH4) and HO2 for the conversion of active chlorine in the stratosphere to the inactive reservoir HCl. Chlorine will thus be a less efficient destroyer of stratospheric ozone than previously believed. One-dimensional eddy-diffusion photochemical model calculations indicate that the eventual ozone depletion for a steady-state chlorfluoromethane release at 1975 rates (750,000 tons/year) will be lowered from 20% to 18.5% by the inclusion of this reaction.

Stief, L. J.↗
NASA NTRS1978

Absolute rate of the reaction of hydrogen atoms with ozone from 219-360 K

Absolute rate constants for the reaction of atomic hydrogen with ozone were obtained over the temperature range 219-360 K by the flash photolysis-resonance fluorescence (FP-RF) technique. The results can be expressed in Arrhenius form by k = (1.33 + or - 0.32) times (10 to the minus tenth power) exp(-449 + or - 58/T) cu cm/molecule per sec (two standard deviations). The present work is compared to two previous determinations and is theoretically discussed.

Lee, J. H.↗
NASA NTRS1978

The reaction Cl + H2CO yields HCl + HCO: Decreased sensitivity of stratospheric ozone to chlorine perturbations

The absolute rate constant for the reaction Cl + H2CO yields HCl + HCO was determined by the flash-photolysis resonance fluorescence method to be 7.5 plus or minus 0.9 (2 sigma) times 10 to the minus 11th power cu cm/molecule sec at 298 K and to have a negligible temperature dependence. This rate which is more than 2000 times faster than the rate of Cl + CH4 indicates that formaldehyde (H2CO) will compete significantly with methane (CH4) for the conversion of active chlorine in the stratosphere to the inactive reservoir HCl. Chlorine will thus be a less efficient destroyer of stratosphere ozone than previously believed. Ambient stratospheric ozone will depend less on the ambient chlorine amount and the predicted response to chlorine perturbations will be lessened. One-dimensional eddy-diffusion photochemical model calculations indicate a factor of 1.1 less sensitivity to chlorine than recently reported. For a steady-state CFM release at 1975 rates (750,000 tons/year) the eventual ozone depletion is now calculated to be 14%.

Stief, L. J.↗