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Watson, R. T.

Publications and source records attributed to Watson, R. T..

36 records · Page 2
All sourcesNASA NTRSDOE OSTI
NASA NTRS1980

Temperature dependence of the reaction O/3P/ + OH/2 Pi/ yields O2 + H

Measurements of the absolute rate and temperature dependence of the rate constant for the reaction of ground state atomic oxygen with hydroxyl radicals to yield molecular oxygen and hydrogen atoms over the temperature range 211-499 K are presented. The reaction was monitored in a low-pressure discharge flow resonance fluorescence apparatus under pseudo-first-order conditions in which the oxygen concentration was greater than the hydroxyl concentration. An expression for the temperature dependence of the rate constant is derived from a least-squares fit to the observed bimolecular rate constants, which were found to range from 3.21 to 2.77 x 10 to the -11th cu cm/molecule per sec for temperatures from 211 to 499 K, indicative of a slight negative temperature dependence. Results are compared with those of previous workers, and the significance of the lower value of the rate constant obtained in the present study to models of HO(x) in the upper stratosphere is indicated.

Lewis, R. S.↗
NASA NTRS1980

Kinetics studies of the reactions of CH3O2 with NO, NO2, and CH3O2 at 298 K

Rate constants for the reactions of CH3O2 with NO, NO2, and CH3O2 at 298 K were measured by using the FP/UV technique. The disappearance of CH3O2 was observed over a wide range of reactant concentrations and total pressure. It is shown that the reaction of CH3O2 with NO2 is still in the falloff region at 700 torr and that the high-pressure limit is attained only at pressures exceeding several atmospheres.

Sander, S. P.↗
NASA NTRS1980

Kinetics study of the Cl/2P/ + Cl2O yields Cl2 + ClO reaction at 298 K

The kinetics of the Cl + Cl2O reaction, a possible source of ClO(2 Pi) radicals for atmospheric photochemical studies, are investigated at 298 K. The discharge flow/mass spectrometry and discharge flow/resonance fluorescence techniques were used to monitor the decay of C12O in the presence of excess concentrations of atomic chlorine and chlorine monoxide, respectively. The pseudo-first order rate constants obtained from both experiments are found to be in excellent agreement, averaging 9.8 + or - 0.8 x 10 to the -11th cu cm/molecule per sec. Results are consistent with the lower limit obtained by Edgecombe et al. (1957) but differ by a factor of 150 from those of Basco and Dogra (1971). The present value is also noted to be consistent with a lower value for the rate constant of the reaction of oxygen atoms with Cl2O.

Ray, G. W.↗
NASA NTRS1980

Ozone photolysis - Determination of the O/3P/ quantum yield at 266 nm

Direct production of O(3P) from the photodissociation of O3 at 266 nm has been observed by time-resolved resonance fluorescence following laser flash photolysis. The quantum yield for O(3P) production was determined to be 0.12 + or - 0.02 at this wavelength. This result confirms the qualitative observations of two previous photofragment studies and establishes an absolute value of the quantum yield for O(1D) production of 0.88. This value has been used as a basis for normalizing relative quantum yields in the fall-off region, and interpreting O(1D) kinetics studies.

Brock, J. C.↗
NASA NTRS1980

Atmospheric bromine and ozone perturbations in the lower stratosphere

The role of bromine compounds in the photochemistry of the natural and perturbed stratosphere has been reexamined using an expanded reaction scheme and the results of recent laboratory studies of several key reactions. The most important finding is that through the reaction BrO + ClO yielding Br + Cl + O2 there is a synergistic effect between bromine and chlorine which results in an efficient catalytic destruction of ozone in the lower stratosphere. One-dimensional photochemical model results indicate that BrO is the major bromine species throughout the stratosphere, followed by BrONO2, HBr, HOBr and Br. It is shown from the foregoing that bromine is more efficient than chlorine as a catalyst for destroying ozone, and the implications for stratospheric ozone of possible future growth in the industrial and agricultural use of bromine are discussed. Bromine concentrations of 20 pptv (2 x 10 to the -11th power), as suggested by recent observations, can decrease the present-day integrated ozone column density by 2.4%, and can enhance ozone depletion from steady-state chlorofluoromethane release at 1973 rates by a factor of 1.1-1.2.

Yung, Y. L.↗
NASA NTRS1980

Laser flash photolysis of ozone - O/1D/ quantum yields in the fall-off region 297-325 nm

The wavelength dependence of the quantum yield for O(1D) production from ozone photolysis has been determined between 297.5 nm and 325 nm in order to resolve serious discrepancies among previous studies. The results of this investigation are compared to earlier work by calculating atmospheric production rate constants for O(1D). It is found that for the purpose of calculating this rate constant, there is now good agreement among three studies at 298 K. Furthermore, it appears that previous data on the temperature dependence of the O(1D) quantum yield fall-off is adequate for determining the vertical profile of the O(1D) production rate constant. Several experimental difficulties associated with using NO2(asterisk) chemiluminescence to monitor O(1D) have been identified.

Brock, J. C.↗
NASA NTRS1980

Evaluated kinetic and photochemical data for atmospheric chemistry

This paper contains a critical evaluation of the kinetics and photochemistry of gas phase chemical reactions of neutral species involved in middle atmosphere chemistry (10-55 km altitude). Data sheets have been prepared for 148 thermal and photochemical reactions, containing summaries of the available experimental data with notes giving details of the experimental procedures. For each reaction a preferred value of the rate coefficient at 298 K is given together with a temperature dependency where possible. The selection of the preferred value is discussed, and estimates of the accuracies of the rate coefficients and temperature coefficients have been made for each reaction. The data sheets are intended to provide the basic physical chemical data needed as input for calculations which model atmospheric chemistry. A table summarizing the preferred rate data is provided, together with an appendix listing the available data on enthalpies of formation of the reactant and product species.

Baulch, D. L.↗
NASA NTRS1979

Pressure and temperature dependence kinetics study of the NO + BrO yielding NO2 + Br reaction - Implications for stratospheric bromine photochemistry

The reactivity of NO with BrO radicals over a wide range of pressure (100-700 torr) and temperature (224-398 K) is investigated using the flash photolysis-ultraviolet absorption technique. The flash photolysis system consists of a high-pressure xenon arc light source, a reaction cell/gas filter/flash lamp combination, and a 216.5 half-meter monochromator/polychromator/spectrography for wavelength selectivity. The details of the reaction and its corresponding Arrhenius expression are identified. The results are compared with previous measurements, and atmospheric implications of the reaction are discussed. The NO + BrO yielding NO2 + Br reaction is shown to be important in controlling the concentration ratios of BrO/Br and BrO/HBr in the stratosphere, but this reaction does not affect the catalytic efficiency of BrOx in ozone destruction.

Watson, R. T.↗
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

An assessment of an F2 or N2O4 atmospheric injection from an aborted space shuttle mission

Assuming a linear relationship between the stratosphere loading of NOx and the magnitude of the ozone perturbation, the change in ozone expected to result from space shuttle ejection of N2O4 was calculated based on the ozone change that is predicted for the (much greater) NOx input that would accompany large-scale operations of SSTs. Stratospheric fluorine reactions were critically reviewed to evaluate the magnitude of fluorine induced ozone destruction relative to the reduction that would be caused by addition of an equal amount of chlorine. The predicted effect on stratospheric ozone is vanishingly small.

Watson, R. T.↗
NASA NTRS1977

A quantum yield determination of O/1D/ production from ozone via laser flash photolysis

The quantum yield of electronically excited atomic oxygen produced from ozone photolysis was measured at 298 K from wavelengths of 293.0 to 316.5 nm. The reaction of the atomic oxygen with N2O to form excited NO2 was used to monitor the O production; a frequency-doubled flashlamp-pumped dye laser which provided tunable ultraviolet in the desired spectral region with 0.1-nm linewidth served as the photolysis source. The atomic oxygen quantum yield was found to be constant below 300 nm, with a sharp decrease centered at 308 nm and a diminution to less than one tenth of the constant value by 313.5 nm.

Philen, D. L.↗
NASA NTRS1977

High resolution absorption cross sections for the A2Pi-X2Pi system of ClO

High-resolution ultraviolet absorption cross-sections for the ClO molecule are obtained, with the aim of facilitating studies of ozone depletion resulting from the injection of chlorofluorocarbons into the atmosphere. The spectroscopic analysis, which involves a frequency-doubled tunable dye laser with a bandwidth of 0.015 A, is described. Studies of the rotational lines of the ClO A 2Pi 3/2-X2Pi 3/2 9-10 band were conducted. Peak cross-sections for the P and R lines of the 9-0 band are found to be 10.0, 9.6, 8.6, 10.6, 10.3, and 9.2 times ten to the negative seventeenth power cm squared, with estimated accuracy of plus or minus 25%. Problems in distinguishing between Cl-35 and Cl-37 absorption are also considered.

Wine, P. H.↗
NASA NTRS1977

Rate constants for reactions of ClO/x/ of atmospheric interest

Chemical kinetics measurements on 82 gas phase reactions of chlorine containing species are reviewed. Recommended rate constants are given. The principal species of interest are Cl, Cl2, ClO, Cl2O, ClOO, OClO, CINO, HCl and halo derivatives of methane and ethane. Absorption spectra are given for 21 species. In addition the chemical kinetics methods used to obtain these data are discussed with regard to their applicability and reliability.

Watson, R. T.↗