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At least 775 records · Page 43
All sourcesNASA NTRSDOE OSTI
NASA NTRS1980

The lifetime of the OH radical in comets at 1 AU

It has been shown that the photochemical lifetime of OH in comets is a function of the comet's radial velocity. The calculated lifetime at 1 AU can vary between 69,000 and 210,000 sec for radial velocities that vary from -58 to +59 km/sec. A comparison between the scale lengths observed for three comets and those calculated based upon the theoretical lifetime has been made. This comparison shows that in two of the comets the lifetime derived from the scale lengths is a factor of 1.7 larger than the theoretical lifetime. Suggestions are made about the origin of this discrepancy.

Jackson, W. M.↗
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 NTRS1981

Stratospheric hydroxyl radical concentrations - New limitations suggested by observations of gaseous and particulate sulfur

A one-dimensional aerosol model is employed in investigating the sensitivity of the stratospheric distributions of gaseous sulfur compounds and sulfate aerosol particles to changes in OH and CS2 concentrations, in eddy diffusion coefficients, and in important chemical rate constants. By comparing model predictions with recent observational data for SO2, OCS, and particulates, it is found that, with regard to atmospheric sulfur, CS2 is only a secondary source of sulfur for the stratosphere relative to OCS and that background tropospheric CS2 concentrations by volume are likely to be less than 70 parts per trillion. It is also established that under stratospheric conditions the rate coefficients for the reactions of OH with OCS and CS2 may be substantially smaller than the room temperature laboratory values of Kurylo (1978).

Turco, R. P.↗
NASA NTRS1981

Kinetics and mechanism of the disproportionation of BrO radicals

In the reported investigation, measurements were conducted of the rate constant for the reaction BrO + BrO yields products (1), taking into account the temperature range from 223 to 338 K and the pressure range from 50 to 475 torr of He. The flash photolysis-ultraviolet absorption technique was employed in the experiments. Two independent approaches were used to determine the relative rates of the two reaction branches, BrO + BrO yields BrOO + Br (1a), and BrO + BrO yields Br2 + O2 (1b), one dependent and the other independent of the BrO absorption cross section with the results being in excellent agreement. The rate constant, k(1), was found to be independent of pressure.

Sander, S. P.↗
NASA NTRS1981

The feasibility of using time-dependent photochemical calculations to infer radical species concentrations from solar occultation absorption measurements

In connection with fast chemical reactions, short-lived stratospheric species experience rapid concentration variations at sunset and sunrise. For solar occultation absorption measurements, these rapid concentration variations may introduce significant errors with respect to the inference of atmospheric abundances for some species due to asymmetrical concentration distributions. Most retrieval algorithms assume that concentration distributions are spherically symmetric. The effect of this assumption on the accuracy of inferred concentrations has been studied by Kerr et al. (1977). The present investigation considers the feasibility of using a time-dependent one-dimensional photochemical model to provide detailed information about the asymmetrical distribution for use in the retrieval procedure. As shown by Boughner et al. (1980), diurnal effects can be represented by an inhomogeneity factor. It is found that the NO retrieval improves considerably with the inclusion of a correction factor containing the asymmetrical variations.

Larsen, J. C.↗
NASA NTRS1983

Laboratory and astronomical measurement of the millimeter wave spectrum of the ethynyl radical CCH

The N = 0 yields 1 and 1 yields 2 rotational transitions of CCH at 87 and 174 GHz, respectively, have been detected in a laboratory glow discharge in a mixture of He and C2H2. The spectroscopic constants of CCH derived from measurements of the hfs of the transitions agree well with those derived from astronomical observations, confirming the astronomical detection of CCH. As the CCH lines in the Orion Nebula are narrower than the laboratory lines but less certain in rest frequency owing to uncertainty in the radial velocity, the most accurate values for the spectroscopic constants of CCH are obtained from a simultaneous fit of both the laboratory and astronomical data. For the rotation, centrifugal distortion, spin-rotation, and hyperfine constants, respectively, the values found are within 0.006 of 43674.534 MHz, within 0.0008 of 0.1071 MHz, within 0.004 of -62.606 MHz, b = within 0.019 MHz of 40.426, and c is within 0.026 of 12.254 MHz.

Gottlieb, C. A.↗
NASA NTRS1983

The microwave and far-infrared spectra of the CH radical

The frequencies, wavelengths, and line strengths for transitions of the CH molecule at microwave and far-infrared wavelengths have been calculated from an analysis of the laser magnetic resonance spectrum. The low-frequency transitions are between lambda-type doublets, while the higher frequency transitions are between different spin-rotation levels.

Brown, J. M.↗
NASA NTRS1983

Comments on laser-excited fluorescence of the hydroxyl radical: Relaxation coefficients at atmospheric pressure, appendix 5

The lifetime of the excited state of a atom or molecule is often determined from the rate of fluorescence decay originating as a function of buffer gas pressure, an accurate determination is made of the rates of collision induced transitions away from the excited state. Deconvolution can in principle be employed to resolve fluorescence times shorter than the response times of the system. However, attainable reproducibility and accuracy in actual experiments usually set a limit beyond which no meaningful results are expected. Prudence thus dictates that the results of deconvolution be viewed with extreme caution whenever fluorescence time much shorter than the response of times of the system are indicated.

Wang, C. C.↗
NASA NTRS1983

The photodissociation lifetimes of the OH and OD radicals in comets

The photodissociation rates of OH and OD molecules due to absorption of solar radiation in the X(2)Pi-A(2)Sigma(+) electronic transition are calculated to lie between 3.5 and 6.7 x 10 to the -6th/sec for OH for heliocentric velocities between -60 and +60 km/sec and at about 4.7 x 10 to the -7th/sec for OD at 1 AU from the sun. The corresponding lifetimes, which are upper bounds to the actual lifetimes, are generally consistent with the observational cometary data.

Singh, P. D.↗
NASA NTRS1984

Infrared and far-infrared transition frequencies for the CH2 radical

A list of frequencies and intensities for transitions of CH2 in the middle and far infrared regions is presented which should aid in the detection of CH2 and provide valuable information on the local physical and chemical environment. Results are presented for frequency, vacuum wavelength, and line strength for rotational transition frequencies and for the transition frequencies of the v(2) band.

Sears, T. J.↗
NASA NTRS1984

A measurement of the vibrational band strength for the v3 band of the HO2 radical

Laboratory measurements of the v(3) band strength of HO2 using a tunable diode laser to measure the absorption strength of a vibration-rotation line in the P branch near 1080/cm are reported. The HO2 is generated in a discharge-flow system by reaction of fluorine atoms with excess H2O2: F + H2O2 - HO2 + HF. The HO2 concentration is determined from measurements of F-atom concentrations using both chemical titration with Cl2 and tunable diode laser absorption by the F-atom spin-orbit transition near 404/cm. The experimental data are consistent with a value of k(3) = (1.6 + or - 0.3) x 10 to the 12th cu cm/s and a ratio k(4)/k(1) = 1.0 + or - 0.4. The line strength for the 6(15) - 7(16)F(1) transition is 2.9 x 10 to the -21 sq cm/molecule/cm, which corresponds to a v(3) band strength of 35 + or - 9/sq cm/(STP atm). This value is a factor of 1.6 to 6 lower than previous ab initio calculations.

Zahniser, M. S.↗
NASA NTRS1984

Mechanism of the atmospheric oxidation of sulfur dioxide - Catalysis by hydroxyl radicals

A flash photolysis/resonance fluorescence technique was used to investigate the decay of OH due to the reaction OH + SO2 (+M) to HOSO2 (+M). In the presence of small amounts of NO (10 to the 14th per cu cm), the decays deviated from the normal semilogarithmic linearity due to reformation of OH. On the basis of computer simulations of the decay curves, it is suggested that the reactions HOSO2 + O2 to HO2 + SO3 (k3), and HO2 + HO to OH + NO2 are the likely subsequent steps in SO2 oxidation. The upper limit for the binding energy of HOSO2 relative to OH + SO2 is estimated to be 32 kcal/mol. The atmospheric implications of a catalytic oxidation mechanism are briefly discussed.

Margitan, J. J.↗
NASA NTRS1985

The microwave and far-infrared spectra of the SiH radical

Consideration of Si's cosmic abundance leads to the expectation that the related molecule SiH may be detected in extraterrestrial sources. A tabulation is presented of frequencies, wavelengths, and line strengths for SiH molecule transitions at microwave and far-IR wavelengths, on the basis of an analysis of its laser magnetic resonance spectrum. It is hoped that the frequencies presented will be useful to both laboratory spectroscopists and astrophysicists.

Brown, J. M.↗