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Stief, L. J.

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

At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
NASA NTRS1978

Absolute rate of the reaction of bromine atoms with ozone from 200-360 K

The rate constant for the reaction Br + O3 yields BrO + O2 was measured from 200 to 360 K by the technique of flash photolysis coupled to time resolved detection of bromine atoms by resonance fluorescence (FP-RF). Br atoms were produced by the flash photolysis of CH3Br at lambda 165nm.O3 was monitored continuously under reaction conditions by absorption at 253.7 nm. At each of five temperatures the results were independent of substantial variations in O3, total pressure and limited variations in flash intensity. The measured rate constants obeyed the Arrhenius expression, where the error quoted is two standard deviations. Results are compared with previous determinations which employed the discharge flow-mass spectrometric technique.

Michael, J. V.↗
NASA NTRS1977

Absolute rate constant for the reaction of atomic chlorine with hydrogen peroxide vapor over the temperature range 265-400 K

Rate constants for the reaction of atomic chlorine with hydrogen peroxide were measured from 265-400 K using the flash photolysis-resonance fluorescence technique. Analytical techniques were developed to measure H2O2 under reaction conditions. Due to ambiguity in the interpretation of the analytical results, the data combine to give two equally acceptable representations of the temperature dependence. The results are compared to previous work at 298 K and are theoretically discussed in terms of the mechanism of the reaction. Additional experiments on the H + H2O2 reaction at 298 and 359 K are compared with earlier results from this laboratory and give a slightly revised bimolecular rate constant.

Michael, J. V.↗
NASA NTRS1977

Absolute rate of the reaction of Cl/2P/ with methane from 200-500 K

Rate constants for the reaction Cl + CH4 yields HCl + CH3 were measured in the range 200-500 K by the plot flash photolysis-resonance fluorescence technique. An Arrhenius plot of the mean rate constant observed at 14 equally spaced temperatures is best fit by the expression k = 5.44 times 10 to the minus 19th times T to the exponent 2.50 times exp(-608/T) cu cm per molecule per sec. Appropriate expressions are also given for the rate constant in the two ranges 200-299 K and 299-500 K. These results are compared with a number of other existing determinations of the rate constant by other methods and in different temperature ranges. Most discrepancies are attributed to the nonlinear Arrhenius behavior.

Whytock, D. A.↗
NASA NTRS1976

Absolute rate of the reaction of Cl(p-2) with molecular hydrogen from 200 - 500 K

Rate constants for the reaction of atomic chlorine with hydrogen are measured from 200 - 500 K using the flash photolysis-resonance fluorescence technique. The results are compared with previous work and are discussed with particular reference to the equilibrium constant for the reaction and to relative rate data for chlorine atom reactions. Theoretical calculations, using the BEBO method with tunneling, give excellent agreement with experiment.

Whytock, D. A.↗
NASA NTRS1976

Absolute rate of the reaction of C l(2P) with methane from 200-500 K

Rate constants for the reaction of atomic chlorine with methane have been measured from 200-500K using the flash photolysis-resonance fluorescence technique. When the results from fourteen equally spaced experimental determinations are plotted in Arrhenius form a definite curvature is noted. The results are compared to previous work and are theoretically discussed.

Whytock, D. A.↗
NASA NTRS1976

Absolute rate of the reaction of O/3-P/ with hydrogen sulfide over the temperature range 263 to 495 K

The technique of flash photolysis coupled with time resolved detection of O via resonance fluorescence has been used to obtain rate constants for the reaction of O(3-P) with H2S at temperatures from 263 to 495 K and at pressures in the range 10-400 torr. Under conditions where secondary reactions are avoided, the measured rate constants for the primary step obey the Arrhenius equation k = (7.24 plus or minus 1.07) x 10 to the -12th exp(-3300 plus or minus 100/1.987 T) cu cm/molecules/s. Experiments with D2S show that the reaction exhibits a primary isotope effect, in support of a hydrogen abstraction mechanism.

Whytock, D. A.↗
NASA NTRS1976

Rate of the reaction of atomic hydrogen with propyne over an extended pressure and temperature range

The technique of flash photolysis coupled with time resolved detection of H via resonance fluorescence has been used to obtain rate constants for the reaction of atomic hydrogen with propyne at temperatures from 215 to 460 K and at pressures in the range 5-600 torr. The rate constants are strongly pressure dependent and the high pressure limiting values give rise to the Arrhenius expression K = approximately 6 x 10 to the minus 11th exp(-2450T) cu cm per molecule per sec. The results are discussed and compared with those of previous studies

Whytock, D. A.↗
NASA NTRS1976

Absolute rate parameters for the reaction of atomic hydrogen with hydrazine

Absolute rate parameters for the reaction of atomic hydrogen with hydrazine H + N2H4 yields H2 + N2H3 have been determined in a direct manner using flash photolysis of dilute mixtures of hydrazine in helium and time dependent observation of H via resonance fluorescence. By measuring the H-atom decay under pseudo-first-order conditions, the bimolecular rate constant K sub 1 was obtained over the temperature range 228-400 K. The data were fitted with good linearity to the Arrhenius expression K sub 1 = (9.87 plus or minus 1.17) x 10 to the -12th exp(-2380 plus or minus 100/RT) cu cm/molecule/s. The data were shown to be free of any contributions from secondary reactions involving H as a reactant or product.

Stief, L. J.↗
NASA NTRS1976

Absolute rate parameters for the reaction of ground state atomic oxygen with dimethyl sulfide and episulfide

It is pointed out that the investigated reaction of oxygen with dimethyl sulfide may play an important role in photochemical smog formation and in the chemical evolution of dense interstellar clouds. Kinetic data were obtained with the aid of the flash photolysis-resonance fluorescence method. The photodecomposition of molecular oxygen provided the oxygen atoms for the experiments. The decay of atomic oxygen was studied on the basis of resonance fluorescence observations. Both reactions investigated were found to be fast processes. A negative temperature dependence of the rate constants for reactions with dimethyl sulfide was observed.

Lee, J. H.↗
NASA NTRS1975

Relative quantum yield for the production of O-atom and S-atom from the photodissociation of OCS in the vacuum UV

The relative efficiencies for two dissociative channels in the vacuum UV photolysis of carbonyl sulphide have been determined using the flash photolysis-resonance fluorescence technique to measure initial yields of atomic oxygen and atomic sulphur. At wavelengths above 105 nm, the dissociation of OCS to form atomic sulphur exceeded that for the formation of atomic oxygen to such an extent that only an upper limit could be placed on the minor process. In addition, the flash photo-excitation of carbonyl sulphide produced a long-lived spontaneous emission in the UV and vacuum UV that might be due to molecular fluorescence from OCS.

Klemm, R. B.↗
NASA NTRS1975

A flash photolysis-resonance fluorescence study of the formation of O/1D/ in the photolysis of water and the reaction of O/1D/ with H2, Ar, and He

The technique employed in the study utilizes the vacuum ultraviolet flash photolysis of H2O combined with time resolved, simultaneous detection of H and O via resonance fluorescence at 121.6 and 130.2 nm respectively. The measurements were made by means of photon counting and multichannel scaling. The sensitivity of the system for H and O is discussed. Experiments are reported in which signals due to H and O were accumulated from the flash photolysis of a mixture of 0.1 torr H2O and 100 torr Ar. Attention is given to the relative importance of two primary processes in the photolysis of water.

Stief, L. J.↗
NASA NTRS1974

Absolute rate parameters for the reaction of ground state atomic oxygen with carbonyl sulfide

The rate parameters for the reaction of O(3P) with carbonyl sulfide, O(3P) + OCS yields CO + SO, have been determined directly by monitoring O(3P) using the flash photolysis-resonance fluorescence technique. The value for reaction rate was measured over a temperature range of 263-502 K and the data were fitted to an Arrhenius expression with good linearity. A comparison of the present results with those from previous studies of this reaction is also presented.

Klemm, R. B.↗
NASA NTRS1974

A flash photolysis-resonance fluorescence study of the formation of O(D-1) in the photolysis of water and reaction of O(D-1) with H2, Ar and He

The relative importance of two primary processes in the photolyis of water: (1) H2O + h (nu) yields H + OH, and (2) H2O + h (nu) yields H2 + OD-1 were determined in a direct manner by time resolved detection (via resonance fluorescence) of H and O formed in processes 1 and 2 respectively. The initially formed OD-1 was deactivated to ground state OP-3 prior to detection via resonance fluorescence. The relative quantum yields for processes 1 and 2 are 0.89 and 0.11 for the wavelength interval 105 to 145nm and = to or greater than 0.99, and = to or less than 0.01 for the wavelength interval 145 to 185nm. Rate constants at 300 K for the reactions OD-1 + H2, + Ar, and + He are presented.

Stief, L. J.↗