Photochemistry of Ozone
Photochemical reactions for mesospheric oxygen, oxygen-hydrogen, and oxygen-hydrogen-nitrogen atmospheres calculated for atomic oxygen/ozone ratios
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Photochemical reactions for mesospheric oxygen, oxygen-hydrogen, and oxygen-hydrogen-nitrogen atmospheres calculated for atomic oxygen/ozone ratios
Resonance fluorescence techniques for determining upper atmosphere hydroxyl radical
Radiation induced photochemical reactions in polyisoprene and polybutadiene thin films including microstructural changes
Vacuum ultraviolet photoionization and photodissociation of associated and polymeric systems of liquid water and alcohols
A quantitative discussion is presented of the lifetime against photodecomposition, or the probability of photodecomposition, of interstellar molecules. In addition to photodissociation, molecules can also be destroyed by interaction with high energy radiation and energetic particles. These processes are much less effective than destruction by ultraviolet radiation. However, when the ultraviolet is highly attenuated in clouds, the energetic radiation and particles will persist and will become relatively more important and the ultimate lifetimes in clouds may depend upon these processes.
The mechanisms of the direct photochemical reactions which occur in unsaturated polymers when irradiated as thin films in vacuo are reviewed. Important reactions in 1,4-polyisoprene and 1,4-polybutadiene are cis-trans isomerization, loss of 1,4-unsaturation, formation of new external double bonds (vinylidene and/or vinyl units) and cyclopropyl formation. In 1,2-polybutadiene and 3,4-polyisoprene, on the other hand, the main reaction is consumption of the external double bonds through cyclization. Recent work on the photoinduced microstructural changes in cis and trans polypentenamers is also discussed.
Requirements for determining the source of C3 in comets are discussed, and include high resolution observation of the region near the nucleus, and near-continuous coverage.
The formation processes for C3 or C2 in comets are discussed along with the possibility of trapping the radical inside the clathrates.
Publications are listed covering NASA research from 1966 to 1973. Several major works covering chloroplast reactions, aerobic green algae and hydrogenease, production of molecular hydrogen, and hydrogen and nitrogen metabolism in purple bacteria are summarized.
Gas phase processes involving interstellar molecules are considered. The primary process is photodissociation in the ambient radiation field. In obscured regions, a combination of Johnson's (1965) and Stecher's (1969) Perseus extinction curves was used to obtain the radiation field as a function of the extinction at 5,500 A. On the basis of laboratory measurements, it is concluded that the molecules of water, ammonia, methane, and formaldehyde have lifetimes less than one hundred years.
The atmospheric composition of Mars is presented, and the applicability of laboratory data on CO2 absorption cross sections and quantum yields of dissociation is discussed. A summary and critical evaluation are presented on the various mechanisms proposed for converting the photodissociation products CO and O2 back to CO2.
The possibility of catalytic destruction of H by C2H2 in the Jovian upper atmosphere is investigated, and other photochemical hydrocarbon reactions are presented. It is shown that the catalytic action of C2H2 can destroy or preserve atomic hydrogen, depending on the branching ratio of an intermediate reaction and the temperature dependence of various reaction rates. A model Jovian atmosphere is constructed, and the altitude profiles of some species are plotted. It is noted that this model has a greater atomic hydrogen abundance and a lower concentration of C2H2 than previous ones, and that the H profile should be considered as an upper limit for the Jovian atmosphere.
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An analysis is conducted of experimental data reported by Norrish and Neville (1934) who studied quantum yields for ozone destruction. A reaction scheme is presented for the Cl2-O3 system. It is demonstrated that the reaction scheme provides a quantitative explanation concerning the main features of the experimental data. Attention is given to reactions involving ClO, OClO, ClOO, and ClO3.
Measurements of O(++) concentrations made by the Atmosphere Explorer C satellite are analyzed for altitudes where photochemical equilibrium conditions prevail in order to determine the photochemical sources and sinks of the doubly charged ion. The major loss process is found to be through partial charge exchange with neutral atomic oxygen with a rate coefficient of 1 x 10 to the -11th cu cm/s with an uncertainty of 40%. Above 220 km the major source is photo-ionization of O(+). However, X ray ionization of O (at not greater than 23.3 A) producing O(++) directly through the Auger process provides a better fit to the observed profile at lower altitudes.
A critical analysis is carried out for models which may be fine tuned to give agreement with observational constraints for O2, CO, and O3 in the Martian lower atmosphere and which are in accord also with upper atmospheric data for O and CO. The models have a number of features in common: dynamic mixing must be exceedingly rapid at heights above 90 km; if heterogeneous processes are not assumed to play a major role in the removal of atmospheric CO and O2, mixing must be rapid at heights between 30 and 40 km. The value implied for the diffusion coefficient in this region depends on the assumptions made regarding the rates for reaction of OH with HO2 to form H2O and the rate of reaction of HO2 with itself to form H2O2. If these reaction rates are taken to have values similar to those used in current models of the earth's stratosphere, the eddy diffusion coefficient at 40 km above the Martian surface should be about 5 by 10 to the seventh power sq cm/sec.
Viking measurements of the upper atmosphere of Mars have indicated thermospheric temperatures below 200 K, colder than those originally calculated by remote sensing experiments. It is suggested that dynamical coupling of the upper and lower regions of the Martian atmosphere may account for the variability in thermospheric temperature. The absorption of extreme ultraviolet solar radiation may account for observed ionospheric features, and may provide a source of fast N and O atoms escaping the planet's gravitational field. Measurements of the isotopic composition of O and N may be used to place constraints on models of the evolution of the Martian atmosphere. It is suggested that previous abundance of N2 may have exceeded that of CO2 in the present atmosphere, and that large sources of H2O may exist on the planet. The present degassing rate for nitrogen is felt to be less than the time-averaged degassing rate by at least a factor of 20.