Chemical kinetics and photochemical data for use in stratospheric modeling: Evaluation number 5

Sets of rate constants and photochemical cross sections compiled which were evaluated. The primary application of the data is in the modeling of stratospheric processes on the ozone layer and its possible perturbation by anthropogenic and natural phenomena are emphasized

Chemistry of the CO dimer at low temperatures

Researchers conducted a series of experiments on the chlorine-catalyzed photodecomposition of O sub 3 both in the gas and in inert solvents such as CF sub 4 and CO sub 2 in the temperature range about 190 to 225 K. The liquid medium was chosen in order to minimize possible surface loss of long-lived ClO dimer, and to aid in the stabilization of transient excited intermediates. The mechanism of dimer formation was as follows: (1) Cl sub 2 + hv yields Cl + Cl; (2) Cl + O sub 3 yields ClO + O sub 2; (3) ClO + ClO yields Cl sub 2 O sub 2. The experiments were done in cooled low temperature cells, with irradiation from an Osram high pressure mercury arc, filtered to remove radiation below 325 nm. Spectral analysis was by means of a Cary Model 2200 UV spectrometer. The principal objectives were: (1) to determine the lifetime of the dimer as a function of temperature; (2) to observe spectral changes in the mixtures which could be attributed to dimer or related products; and (3) to observe chemical or photochemical reactions of the dimer

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

Absorption cross sections of the ClO dimer

The absorption cross sections of the ClO dimer, ClOOCl, are important to the photochemistry of ozone depletion in the Antarctic. In this work, new measurements were made of the dimer cross sections at 195 K. the results yield somewhat lower values in the long wavelength region, compared to those currently recommended in the NASA data evaluation (JPL 94-26). The corresponding solar photodissociation rates in the Antarctic are reduced by about 40%

Temperature-Dependent Rate Constants and Substituent Effects for the Reactions of Hydroxyl Radicals With Three Partially Fluorinated Ethers

Rate constants and temperature dependencies for the reactions of OH with CF3OCH3 (HFOC-143a), CF2HOCF2H (HFOC-134), and CF3OCF2H (HFOC-125) were studied using a relative rate technique in the temperature range 298-393 K. The following absolute rate constants were derived: HFOC-143a, 1.9E-12 exp(-1555/T); HFOC-134, 1.9E-12 exp(-2006/T); HFOC-125, 4.7E-13 exp(-2095/T). Units are cm(exp 3)molecule(exp -1) s(exp -1). Substituent effects on OH abstraction rate constants are discussed, and it is shown that the CF3O group has an effect on the OH rate constants similar to that of a fluorine atom. The effects are related to changes in the C-H bond energies of the reactants (and thereby the activation energies) rather than changes in the preexponential factors. On the basis of a correlation of rate constants with bond energies, the respective D(C-H) bond strengths in the three ethers are found to be 102, 104, and 106 kcal/mol, with an uncertainty of about 1 kcal/mol

The atmospheric effects of stratospheric aircraft: A current consensus

In the early 1970's, a fleet of supersonic aircraft flying in the lower stratosphere was proposed. A large fleet was never built for economic, political, and environmental reasons. Technological improvements may make it economically feasible to develop supersonic aircraft for current markets. Some key results of earlier scientific programs designed to assess the impact of aircraft emissions on stratospheric ozone are reviewed, and factors that must be considered to assess the environmental impact of aircraft exhaust are discussed. These include the amount of nitrogen oxides injected in the stratosphere, horizontal transport, and stratosphere/troposphere assessment models are presented. Areas in which improvements in scientific understanding and model representation must be made to reduce the uncertainty in model calculations are identified

Carbon dioxide in the atmosphere: Isotopic exchange with ozone and its use as a tracer in the middle atmosphere

Atmospheric heavy ozone is enriched in the isotopes ^(18)O and ^(17)O. The magnitude of this enhancement, of the order of 100‰, is very large compared with that commonly known in atmospheric chemistry and geochemistry. The heavy oxygen atom in heavy ozone is therefore useful as a tracer of chemical species and pathways that involve ozone or its derived products. As a test of the isotopic exchange reactions, we successfully carry out a series of numerical experiments to simulate the results of the laboratory experiments performed by Wen and Thiemens [1993] on ozone and CO_2. A small discrepancy between the experimental and the model values for ^(17)O exchange is also revealed. The results are used to compute the magnitude of isotopic exchange between ozone and carbon dioxide via the excited atom O(^1D) in the middle atmosphere. The model for ^(18)O is in good agreement with the observed values

Chemical kinetics and photochemical data for use in stratospheric modeling. Evaluation number 6

Evaluated sets of rate constants and photochemical cross sections are presented. The primary application of the data is in the modeling of stratospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena

Isotopic exchange between carbon dioxide and ozone via O(^1D) in the stratosphere

We propose a novel mechanism for isotopic exchange between CO_2 and O_3 via O(^1D) + CO_2 → CO_3^* followed by CO_3^* → CO_2 + O(^3P). A one-dimensional model calculation shows that this mechanism can account for the enrichment in ^(18)O in the stratospheric CO_2 observed by Gamo et al. [1989], using the heavy O_3 profile observed by Mauersberger [1981]. The implications of this mechanism for other stratospheric species and as a source of isotopically heavy CO_2 in the troposphere are briefly discussed

Chemical kinetics and photochemical data for use in stratospheric modeling evaluation Number 8

This is the eighth in a series of evaluated sets of rate constants and photochemical cross sections compiled by the NASA Panel for Data Evaluation. The primary application of the data is in the modeling of stratospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena. Copies of this evaluation are available from the Jet Propulsion Laboratory, Documentation Section, 111-116B, California Institute of Technology, Pasadena, California, 91109